Heat-transfer fluids and use thereof in countercurrent heat exchangers

ABSTRACT

A ternary composition including difluoromethane, 3,3,3-trifluoropropene and a hydrocarbon-derived compound containing at least two fluorine atoms and having a boiling point of between −30 and −18° C., which is selected from 1,1-difluoroethane, 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene. This composition is particularly suitable for use as a heat-transfer fund in the presence of countercurrent heat exchangers.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a divisional of U.S. application Ser. No.13/696,866, filed on Nov. 8, 2012, which is U.S. National Phase ofInternational Application No. PCT/FR2011/050880, filed on Apr. 18, 2011claims the benefit of French Application No. 1053668, filed on May 11,2010. The entire contents of each of U.S. application Ser. No.13/696,866, International Application No. PCT/FR2011/05088, and FrenchApplication No. 1053668 are hereby incorporated herein by reference intheir entirety.

FIELD OF THE INVENTION

The present invention relates to heat-transfer fluids suitable for usein countercurrent heat exchangers.

TECHNICAL BACKGROUND

Fluids based on fluorocarbon compounds are widely used invapor-compression heat-transfer systems, in particular air conditioning,heat pump, refrigeration and freezing devices. These devices have incommon the fact that they are based on a thermodynamic cycle comprisingthe vaporization of the fluid at low pressure (in which the fluidabsorbs heat); the compression of the vaporized fluid up to a highpressure; the condensation of the vaporized fluid to liquid at highpressure (in which the fluid releases heat); and the expansion of thefluid in order to complete the cycle.

Vapor compression heat-transfer systems comprise at least two heatexchangers, one in which the fluid vaporizes, and the other in which itcondenses. Heat exchangers may be of cocurrent type or of countercurrenttype.

The choice of a heat-transfer fluid (which may be a pure compound or amixture of compounds) is dictated, on the one hand, by the thermodynamicproperties of the fluid, and on the other hand, by additionalconstraints. Thus, one particularly important criterion is that of theimpact of the fluid considered on the environment. In particular,chlorinated compounds (chlorofluorocarbons and hydrochlorofluorocarbons)have the disadvantage of damaging the ozone layer. Henceforth, generallynon-chlorinated compounds such as hydrofluorocarbons, fluoroethers andfluoroolefins are therefore preferred to them.

Heat-transfer fluids currently used are HFC-134a, R404a (ternary mixtureof 52% of HFC-143a, 44% of HFC-125 and 4% HFC-134a), R407c (ternarymixture of 52% of HFC-134a, 25% of HFC-125 and 23% of HFC-32) and R410a(binary mixture of 50% of HFC-32 and 50% of HFC-125).

It is, however, necessary to develop other heat-transfer fluids thathave a global warming potential (GWP) lower than that of the fluidsabove, and that have equivalent or improved performance levels.

Document WO 2007/002625 describes compositions based on fluoroolefins,and in particular on HFO-1234yf or on HFO-1234ze, in various uses, andin particular as heat-transfer fluids. The document does not specify thetype of heat exchanger used.

Document WO 2007/126414 describes generally a large variety offluoroolefin-based compositions and a large variety of uses of thesecompositions. The document does not specify the type of heat exchangerused.

Documents WO 2009/107364, WO 2009/110228 and WO 2009/116282 describerefrigeration apparatuses in which the refrigerants used are mixturesbased on HFO-1234yf and on HFC-32, optionally supplemented or replacedwith other compounds, such as HFC-125. The type of heat exchanger usedis not specified.

Document US 2009/0158771 describes the use of a ternary mixturecomprising HFC-32, HFC-134a and HFO-1243zf, in a heat transferapplication. The coefficients of performance that are obtained are lowerthan those of the fluid taken as reference, namely HFC-134a. The type ofheat exchanger used is not specified.

Document WO 2009/150763 describes an air-conditioning apparatus with acountercurrent heat exchanger, in which the heat-transfer fluid is amixture of an HFO-1234 and of HFC-32 or of HFC-41.

Document WO 2010/000993 describes the use of a ternary mixturecomprising HFO-1234yf, HFC-32 and HFC-134a, as a heat-transfer fluid.The document does not specify the type of heat exchanger used.

Document WO 2010/000994 describes the use of a ternary mixturecomprising HFO-1234yf, HFC-32 and HFC-152a, as a heat-transfer fluid.The document does not specify the type of heat exchanger used.

However, there is still a need to develop other heat-transfer fluidsthat have a relatively low GWP and that have good energy performancelevels, in particular in applications using countercurrent heatexchangers.

SUMMARY OF THE INVENTION

The invention relates firstly to a ternary composition comprisingdifluoromethane, 3,3,3-trifluoropropene and a hydrocarbon-derivedcompound containing at least two fluorine atoms and having a boilingpoint of between −30 and −18° C., which is selected from1,1-difluoroethane, 2,3,3,3-tetrafluoropropene and1,3,3,3-tetrafluoropropene.

According to one embodiment, the composition comprises difluoromethane,1,1-difluoroethane and 3,3,3-trifluoropropene, and preferably comprisesfrom 2 to 96% of difluoromethane, from 2 to 96% of 1,1-difluoroethaneand from 2 to 96% of 3,3,3-trifluoropropene, and particularlypreferably:

-   -   from 20 to 70% of difluoromethane, from 2 to 30% of        1,1-difluoroethane and from 2 to 78% of 3,3,3-trifluoropropene,        ideally from 25 to 65% of difluoromethane, from 2 to 15% of        1,1-difluoroethane and from 20 to 78% of 3,3,3-trifluoropropene;        or    -   from 60 to 96% of difluoromethane, from 2 to 20% of        1,1-difluoroethane and from 2 to 20% of 3,3,3-trifluoropropene,        ideally from 80 to 90% of difluoromethane, from 5 to 15% of        1,1-difluoroethane and from 5 to 15% of 3,3,3-trifluoropropene;        or    -   from 2 to 20% of difluoromethane, from 2 to 85% of        1,1-difluoroethane and from 2 to 90% of 3,3,3-trifluoropropene,        ideally from 5 to 15% of difluoromethane, from 5 to 85% of        1,1-difluoroethane and from 10 to 90% of 3,3,3-trifluoropropene;        or    -   from 20 to 60% of difluoromethane, from 2 to 70% of        1,1-difluoroethane and from 2 to 70% of 3,3,3-trifluoropropene,        ideally from 25 to 40% of difluoromethane, from 5 to 65% of        1,1-difluoroethane and from 5 to 70% of 3,3,3-trifluoropropene;        or    -   from 50 to 96% of difluoromethane, from 2 to 30% of        1,1-difluoroethane and from 2 to 30% of 3,3,3-trifluoropropene,        ideally from 65 to 80% of difluoromethane, from 5 to 25% of        1,1-difluoroethane and from 5 to 30% of 3,3,3-trifluoropropene.

According to another embodiment, the composition comprisesdifluoromethane, 3,3,3-trifluoropropene and 2,3,3,3-tetrafluoropropene,preferably from 2 to 96% of difluoromethane, from 2 to 96% of3,3,3-trifluoropropene and from 2 to 96% of 2,3,3,3-tetrafluoropropene,and particularly preferably:

-   -   from 5 to 70% of 2,3,3,3-tetrafluoropropene, from 20 to 60% of        difluoromethane and from 2 to 75% of 3,3,3-trifluoropropene,        ideally from 10 to 70% of 2,3,3,3-tetrafluoropropene, from 25 to        50% of difluoromethane and from 2 to 65% of        3,3,3-trifluoropropene; or    -   from 2 to 40% of 2,3,3,3-tetrafluoropropene, from 58 to 90% of        difluoromethane and from 2 to 40% of 3,3,3-trifluoropropene,        ideally from 5 to 30% of 2,3,3,3-tetrafluoropropene, from 65 to        80% of difluoromethane and from 2 to 15% of        3,3,3-trifluoropropene; or    -   from 5 to 75% of 2,3,3,3-tetrafluoropropene, from 2 to 20% of        difluoromethane and from 2 to 90% of 3,3,3-trifluoropropene,        ideally from 5 to 75% of 2,3,3,3-tetrafluoropropene, from 5 to        15% of difluoromethane and from 10 to 90% of        3,3,3-trifluoropropene; or    -   from 5 to 80% of 2,3,3,3-tetrafluoropropene, from 20 to 50% of        difluoromethane and from 2 to 75% of 3,3,3-trifluoropropene,        ideally from 5 to 65% of 2,3,3,3-tetrafluoropropene, from 25 to        30% of difluoromethane and from 2 to 70% of        3,3,3-trifluoropropene; or    -   from 2 to 30% of 2,3,3,3-tetrafluoropropene, from 60 to 90% of        difluoromethane and from 2 to 30% of 3,3,3-trifluoropropene,        ideally from 5 to 25% of 2,3,3,3-tetrafluoropropene, from 65 to        80% of difluoromethane and from 5 to 30% of        3,3,3-trifluoropropene; or    -   from 2 to 30% of 2,3,3,3-tetrafluoropropene, from 68 to 96% of        difluoromethane and from 2 to 20% of 3,3,3-trifluoropropene,        ideally from 8 to 23% of 2,3,3,3-tetrafluoropropene, from 75 to        90% of difluoromethane and from 2 to 10% of        3,3,3-trifluoropropene; or    -   from 2 to 40% of 2,3,3,3-tetrafluoropropene, from 58 to 90% of        difluoromethane and from 2 to 40% of 3,3,3-trifluoropropene,        ideally from 2 to 23% of 2,3,3,3-tetrafluoropropene, from 75 to        90% of difluoromethane and from 2 to 18% of        3,3,3-trifluoropropene.

According to one embodiment, the composition comprises difluoromethane,3,3,3-trifluoropropene and 1,3,3,3-tetrafluoropropene, preferably from 2to 96% of difluoromethane, from 2 to 96% of 3,3,3-trifluoropropene andfrom 2 to 96% of 1,3,3,3-tetrafluoropropene, and particularlypreferably:

-   -   from 25 to 70% of difluoromethane, from 2 to 70% of        3,3,3-trifluoropropene and from 5 to 73% of        1,3,3,3-tetrafluoropropene, ideally from 25 to 50% of        difluoromethane, from 5 to 70% of 3,3,3-trifluoropropene and        from 5 to 55% of 1,3,3,3-tetrafluoropropene; or    -   from 50 to 96% of difluoromethane, from 2 to 50% of        3,3,3-trifluoropropene and from 2 to 50% of        1,3,3,3-tetrafluoropropene, ideally from 65 to 90% of        difluoromethane, from 5 to 30% of 3,3,3-trifluoropropene and        from 5 to 30% of 1,3,3,3-tetrafluoropropene; or    -   from 2 to 25% of difluoromethane, from 2 to 90% of        3,3,3-trifluoropropene and from 5 to 96% of        1,3,3,3-tetrafluoropropene, ideally from 5 to 25% of        difluoromethane, from 5 to 90% of 3,3,3-trifluoropropene and        from 5 to 90% of 1,3,3,3-tetrafluoropropene; or    -   from 20 to 65% of difluoromethane, from 2 to 70% of        3,3,3-trifluoropropene and from 5 to 78% of        1,3,3,3-tetrafluoropropene, ideally from 25 to 50% of        difluoromethane, from 5 to 70% of 3,3,3-trifluoropropene and        from 5 to 70% of 1,3,3,3-tetrafluoropropene; or    -   from 50 to 96% of difluoromethane, from 2 to 48% of        3,3,3-trifluoropropene and from 2 to 30% of        1,3,3,3-tetrafluoropropene, ideally from 65 to 90% of        difluoromethane, from 5 to 30% of 3,3,3-trifluoropropene and        from 5 to 30% of 1,3,3,3-tetrafluoropropene.

According to another embodiment, the composition comprises from 75 to98% of difluoromethane, from 1 to 9% of 1,1-difluoroethane and 1 to 23%of 3,3,3-trifluoropropene.

According to another embodiment, the composition comprises from 70 to98% of difluoromethane, from 1 to 23% of 3,3,3-trifluoropropene and from1 to 28% of 2,3,3,3-tetrafluoropropene.

According to another embodiment, the composition comprises from 75 to98% of difluoromethane, from 1 to 23% of 3,3,3-trifluoropropene and from1 to 10% of 1,3,3,3-tetrafluoropropene.

The invention also relates to the use of the abovementioned composition,as a heat-transfer fluid in a vapor compression circuit.

According to one embodiment, the vapor compression circuit comprises acountercurrent heat exchanger.

The invention also relates to a heat-transfer composition comprising theabovementioned composition as heat-transfer fluid, and one or moreadditives selected from lubricants, stabilizers, surfactants, tracers,fluorescent agents, odorous agents, solubilizing agents and mixturesthereof.

The invention also relates to heat-transfer equipment comprising a vaporcompression circuit containing the abovementioned composition asheat-transfer fluid or containing the abovementioned heat-transfercomposition.

According to one embodiment, the equipment comprises a countercurrentheat exchanger.

According to one embodiment, the equipment is selected from mobile orstationary equipment for heating via a heat pump, for air conditioning,for refrigeration and for freezing.

The invention also relates to a process for heating or cooling a fluidor a body by means of a vapor compression circuit containing aheat-transfer fluid, said process successively comprising theevaporation of the heat-transfer fluid, the compression of theheat-transfer fluid, the condensation of the heat fluid and theexpansion of the heat-transfer fluid, in which the heat-transfer fluidis the composition according to the invention.

According to one embodiment, the abovementioned process is a process forcooling a fluid or a body, in which the temperature of the fluid or ofthe body cooled is from −40° C. to −10° C., and preferably from −35° C.to −25° C., more particularly preferably from −30° C. to −20° C., and inwhich the heat-transfer fluid comprises:

-   -   from 20 to 70% of difluoromethane, from 2 to 30% of        1,1-difluoroethane and from 2 to 78% of 3,3,3-trifluoropropene,        ideally from 25 to 65% of difluoromethane, from 2 to 15% of        1,1-difluoroethane and from 20 to 78% of 3,3,3-trifluoropropene;        or    -   from 60 to 96% of difluoromethane, from 2 to 20% of        1,1-difluoroethane and from 2 to 20% of 3,3,3-trifluoropropene,        ideally from 80 to 90% of difluoromethane, from 5 to 15% of        1,1-difluoroethane and from 5 to 15% of 3,3,3-trifluoropropene;        or    -   from 5 to 70% of 2,3,3,3-tetrafluoropropene, from 20 to 60% of        difluoromethane and 2 to 75% of 3,3,3-trifluoropropene, ideally        from 10 to 70% of 2,3,3,3-tetrafluoropropene, from 25 to 50% of        difluoromethane and from 2 to 65% of 3,3,3-trifluoropropene; or    -   from 2 to 40% of 2,3,3,3-tetrafluoropropene, from 58 to 90% of        difluoromethane and 2 to 40% of 3,3,3-trifluoropropene, ideally        from 5 to 30% of 2,3,3,3-tetrafluoropropene, from 65 to 80% of        difluoromethane and from 2 to 15% of 3,3,3-trifluoropropene; or    -   from 25 to 70% of difluoromethane, from 2 to 70% of        3,3,3-trifluoropropene and from 5 to 73% of        1,3,3,3-tetrafluoropropene, ideally from 25 to 50% of        difluoromethane, from 5 to 70% of 3,3,3-trifluoropropene and        from 5 to 55% of 1,3,3,3-tetrafluoropropene; or    -   from 50 to 96% of difluoromethane, from 2 to 50% of        3,3,3-trifluoropropene and from 2 to 50% of        1,3,3,3-tetrafluoropropene, ideally from 65 to 90% of        difluoromethane, from 5 to 30% of 3,3,3-trifluoropropene and        from 5 to 30% of 1,3,3,3-tetrafluoropropene; or    -   from 2 to 30% of 2,3,3,3-tetrafluoropropene, from 68 to 96% of        difluoromethane and from 2 to 20% of 3,3,3-trifluoropropene,        ideally from 8 to 23% of 2,3,3,3-tetrafluoropropene, from 75 to        90% of difluoromethane and from 2 to 10% of        3,3,3-trifluoropropene.

According to another embodiment, the abovementioned process is a processfor cooling a fluid or a body, in which the temperature of the fluid orof the body cooled is from −15° C. to 15° C., and preferably from −10°C. to 10° C., more particularly preferably from −5° C. to 5° C., and inwhich the heat-transfer fluid comprises:

-   -   from 2 to 20% of difluoromethane, from 2 to 85% of        1,1-difluoroethane and from 2 to 90% of 3,3,3-trifluoropropene,        ideally from 5 to 15% of difluoromethane, from 5 to 85% of        1,1-difluoroethane and from 10 to 90% of 3,3,3-trifluoropropene;        or    -   from 20 to 60% of difluoromethane, from 2 to 70% of        1,1-difluoroethane and from 2 to 70% of 3,3,3-trifluoropropene,        ideally from 25 to 40% of difluoromethane, from 5 to 65% of        1,1-difluoroethane and from 5 to 70% of 3,3,3-trifluoropropene;        or    -   from 50 to 96% of difluoromethane, from 2 to 30% of        1,1-difluoroethane and from 2 to 30% of 3,3,3-trifluoropropene,        ideally from 65 to 80% of difluoromethane, from 5 to 25% of        1,1-difluoroethane and from 5 to 30% of 3,3,3-trifluoropropene;        or    -   from 5 to 75% of 2,3,3,3-tetrafluoropropene, from 2 to 20% of        difluoromethane and from 2 to 90% of 3,3,3-trifluoropropene,        ideally from 5 to 75% of 2,3,3,3-tetrafluoropropene, from 5 to        15% of difluoromethane and from 10 to 90% of        3,3,3-trifluoropropene; or    -   from 5 to 80% of 2,3,3,3-tetrafluoropropene, from 20 to 50% of        difluoromethane and from 2 to 75% of 3,3,3-trifluoropropene,        ideally from 5 to 65% of 2,3,3,3-tetrafluoropropene, from 25 to        35% of difluoromethane and from 2 to 70% of        3,3,3-trifluoropropene; or    -   from 2 to 30% of 2,3,3,3-tetrafluoropropene, from 60 to 90% of        difluoromethane and from 2 to 30% of 3,3,3-trifluoropropene,        ideally from 5 to 25% of 2,3,3,3-tetrafluoropropene, from 65 to        80% of difluoromethane and from 5 to 30% of        3,3,3-trifluoropropene; or    -   from 2 to 25% of difluoromethane, from 2 to 90% of        3,3,3-trifluoropropene and from 5 to 96% of        1,3,3,3-tetrafluoropropene, ideally from 5 to 25% of        difluoromethane, from 5 to 90% of 3,3,3-trifluoropropene and        from 5 to 90% of 1,3,3,3-tetrafluoropropene; or    -   from 20 to 65% of difluoromethane, from 2 to 70% of        3,3,3-trifluoropropene and from 5 to 78% of        1,3,3,3-tetrafluoropropene, ideally from 25 to 50% of        difluoromethane, from 5 to 70% of 3,3,3-trifluoropropene and        from 5 to 70% of 1,3,3,3-tetrafluoropropene; or    -   from 50 to 96% of difluoromethane, from 2 to 48% of        3,3,3-trifluoropropene and from 2 to 30% of        1,3,3,3-tetrafluoropropene, ideally from 65 to 90% of        difluoromethane, from 5 to 30% of 3,3,3-trifluoropropene and        from 5 to 30% of 1,3,3,3-tetrafluoropropene; or    -   from 2 to 40% of 2,3,3,3-tetrafluoropropene, from 58 to 90% of        difluoromethane and from 2 to 40% of 3,3,3-trifluoropropene,        ideally from 2 to 23% of 2,3,3,3-tetrafluoropropene, from 75 to        90% of difluoromethane and from 2 to 18% of        3,3,3-trifluoropropene.

According to another embodiment, the abovementioned process is a processfor heating a fluid or a body, in which the temperature of the fluid orof the body heated is from 30° C. to 80° C., and preferably from 35° C.to 55° C., more particularly preferably from 40° C. to 50° C., in whichthe heat-transfer fluid comprises:

-   -   from 2 to 20% of difluoromethane, from 2 to 85% of        1,1-difluoroethane and from 2 to 90% of 3,3,3-trifluoropropene,        ideally from 5 to 15% of difluoromethane, from 5 to 85% of        1,1-difluoroethane and from 10 to 90% of 3,3,3-trifluoropropene;        or    -   from 20 to 60% of difluoromethane, from 2 to 70% of        1,1-difluoroethane and from 2 to 70% of 3,3,3-trifluoropropene,        ideally from 25 to 40% of difluoromethane, from 5 to 65% of        1,1-difluoroethane and from 5 to 70% of 3,3,3-trifluoropropene;        or    -   from 50 to 96% of difluoromethane, from 2 to 30% of        1,1-difluoroethane and from 2 to 30% of 3,3,3-trifluoropropene,        ideally from 65 to 80% of difluoromethane, from 5 to 25% of        1,1-difluoroethane and from 5 to 30% of 3,3,3-trifluoropropene;        or    -   from 5 to 75% of 2,3,3,3-tetrafluoropropene, from 2 to 20% of        difluoromethane and from 2 to 90% of 3,3,3-trifluoropropene,        ideally from 5 to 75% of 2,3,3,3-tetrafluoropropene, from 5 to        15% of difluoromethane and from 10 to 90% of        3,3,3-trifluoropropene; or    -   from 5 to 80% of 2,3,3,3-tetrafluoropropene, from 20 to 50% of        difluoromethane and from 2 to 75% of 3,3,3-trifluoropropene,        ideally from 5 to 65% of 2,3,3,3-tetrafluoropropene, from 25 to        35% of difluoromethane and from 2 to 70% of        3,3,3-trifluoropropene; or    -   from 2 to 35% of 2,3,3,3-tetrafluoropropene, from 60 to 90% of        difluoromethane and from 2 to 30% of 3,3,3-trifluoropropene,        ideally from 5 to 25% of 2,3,3,3-tetrafluoropropene, from 65 to        80% of difluoromethane and from 5 to 30% of        3,3,3-trifluoropropene; or    -   from 2 to 25% of difluoromethane, from 2 to 90% of        3,3,3-trifluoropropene and from 5 to 96% of        1,3,3,3-tetrafluoropropene, ideally from 5 to 25% of        difluoromethane, from 5 to 90% of 3,3,3-trifluoropropene and        from 5 to 90% of 1,3,3,3-tetrafluoropropene; or    -   from 20 to 65% of difluoromethane, from 2 to 70% of        3,3,3-trifluoropropene and from 5 to 78% of        1,3,3,3-tetrafluoropropene, ideally from 25 to 50% of        difluoromethane, from 5 to 70% of 3,3,3-trifluoropropene and        from 5 to 70% of 1,3,3,3-tetrafluoropropene; or    -   from 50 to 96% of difluoromethane, from 2 to 48% of        3,3,3-trifluoropropene and from 2 to 30% of        1,3,3,3-tetrafluoropropene, ideally from 65 to 90% of        difluoromethane, from 5 to 30% of 3,3,3-trifluoropropene and        from 5 to 30% of 1,3,3,3-tetrafluoropropene; or    -   from 2 to 40% of 2,3,3,3-tetrafluoropropene, from 58 to 90% of        difluoromethane and from 2 to 40% of 3,3,3-trifluoropropene,        ideally from 2 to 23% of 2,3,3,3-tetrafluoropropene, from 75 to        90% of difluoromethane and from 2 to 18% of        3,3,3-trifluoropropene.

The invention also relates to a process for reducing the environmentalimpact of heat-transfer equipment comprising a vapor compression circuitcontaining an initial heat-transfer fluid, said process comprising astep of replacing the initial heat-transfer fluid in the vaporcompression circuit with a final transfer fluid, the final transferfluid having a GWP lower than the initial heat-transfer fluid, in whichthe final heat-transfer fluid is a composition according to theinvention.

According to one embodiment of said process for reducing theenvironmental impact, the initial heat-transfer fluid is a ternarymixture of 52% of 1,1,1-trifluoroethane, 44% of pentafluoroethane and 4%of 1,1,1,2-tetrafluoroethane or a ternary mixture of 52% of1,1,1,2-tetrafluoroethane, 25% of pentafluoroethane and 23% ofdifluoromethane, and the final heat-transfer fluid comprises:

-   -   from 20 to 70% of difluoromethane, from 2 to 30% of        1,1-difluoroethane and from 2 to 78% of 3,3,3-trifluoropropene,        ideally from 25 to 65% of difluoromethane, from 2 to 15% of        1,1-difluoroethane and from 20 to 78% of 3,3,3-trifluoropropene;        or    -   from 20 to 60% of difluoromethane, from 2 to 70% of        1,1-difluoroethane and from 2 to 70% of 3,3,3-trifluoropropene,        ideally from 25 to 40% of difluoromethane, from 5 to 65% of        1,1-difluoroethane and from 5 to 70% of 3,3,3-trifluoropropene;        or    -   from 5 to 70% of 2,3,3,3-tetrafluoropropene, from 20 to 60% of        difluoromethane and from 2 to 75% of 3,3,3-trifluoropropene,        ideally from 10 to 70% of 2,3,3,3-tetrafluoropropene, from 25 to        50% of difluoromethane and from 2 to 65% of        3,3,3-trifluoropropene; or    -   from 5 to 80% of 2,3,3,3-tetrafluoropropene, from 20 to 50% of        difluoromethane and from 2 to 75% of 3,3,3-trifluoropropene,        ideally from 5 to 65% of 2,3,3,3-tetrafluoropropene, from 25 to        3% of difluoromethane and from 2 to 70% of        3,3,3-trifluoropropene; or    -   from 25 to 70% of difluoromethane, from 2 to 70% of        3,3,3-trifluoropropene and from 5 to 73% of        1,3,3,3-tetrafluoropropene, ideally from 25 to 50% of        difluoromethane, from 5 to 70% of 3,3,3-trifluoropropene and        from 5 to 55% of 1,3,3,3-tetrafluoropropene; or    -   from 20 to 65% of difluoromethane, from 2 to 70% of        3,3,3-trifluoropropene and from 5 to 78% of        1,3,3,3-tetrafluoropropene, ideally from 25 to 50% of        difluoromethane, from 5 to 70% of 3,3,3-trifluoropropene and        from 5 to 70% of 1,3,3,3-tetrafluoropropene.

According to another embodiment of said process for reducingenvironmental impact, the initial heat-transfer fluid is a binarymixture of 50% of difluoromethane and 50% of pentafluoroethane, and thefinal heat-transfer fluid comprises:

-   -   from 60 to 96% of difluoromethane, from 2 to 20% of        1,1-difluoroethane and from 2 to 20% of 3,3,3-trifluoropropene,        ideally from 80 to 90% of difluoromethane, from 5 to 15% of        1,1-difluoroethane and from 5 to 15% of 3,3,3-trifluoropropene;        or    -   from 50 to 96% of difluoromethane, from 2 to 30% of        1,1-difluoroethane and from 2 to 30% of 3,3,3-trifluoropropene,        ideally from 65 to 80% of difluoromethane, from 5 to 25% of        1,1-difluoroethane and from 5 to 30% of 3,3,3-trifluoropropene;        or    -   from 2 to 40% of 2,3,3,3-tetrafluoropropene, from 58 to 90% of        difluoromethane and from 2 to 40% of 3,3,3-trifluoropropene,        ideally from 5 to 30% of 2,3,3,3-tetrafluoropropene, from 65 to        80% of difluoromethane and from 2 to 15% of        3,3,3-trifluoropropene; or    -   from 2 to 30% of 2,3,3,3-tetrafluoropropene, from 60 to 90% of        difluoromethane and from 2 to 30% of 3,3,3-trifluoropropene,        ideally from 5 to 25% of 2,3,3,3-tetrafluoropropene, from 65 to        80% of difluoromethane and from 5 to 30% of        3,3,3-trifluoropropene; or    -   from 50 to 96% of difluoromethane, from 2 to 50% of        3,3,3-trifluoropropene and from 2 to 50% of        1,3,3,3-tetrafluoropropene, ideally from 65 to 90% of        difluoromethane, from 5 to 30% of 3,3,3-trifluoropropene and        from 5 to 30% of 1,3,3,3-tetrafluoropropene; or    -   from 50 to 96% of difluoromethane, from 2 to 48% of        3,3,3-trifluoropropene and from 2 to 30% of        1,3,3,3-tetrafluoropropene, ideally from 65 to 90% of        difluoromethane, from 5 to 30% of 3,3,3-trifluoropropene and        from 5 to 30% of 1,3,3,3-tetrafluoropropene.

According to one embodiment of said process for reducing environmentalimpact, the initial heat-transfer fluid is 1,1,1,2-tetrafluoroethane,and the final heat-transfer fluid comprises:

-   -   from 2 to 20% of difluoromethane, from 2 to 85% of        1,1-difluoroethane and from 2 to 90% of 3,3,3-trifluoropropene,        ideally from 5 to 15% of difluoromethane, from 5 to 85% of        1,1-difluoroethane and from 10 to 90% of 3,3,3-trifluoropropene;        or    -   from 5 to 75% of 2,3,3,3-tetrafluoropropene, from 2 to 20% of        difluoromethane and from 2 to 90% of 3,3,3-trifluoropropene,        ideally from 5 to 75% of 2,3,3,3-tetrafluoropropene, from 5 to        15% of difluoromethane and from 10 to 90% of        3,3,3-trifluoropropene; or    -   from 2 to 25% of difluoromethane, from 2 to 90% of        3,3,3-trifluoropropene and from 5 to 96% of        1,3,3,3-tetrafluoropropene, ideally from 5 to 25% of        difluoromethane, from 5 to 90% of 3,3,3-trifluoropropene and        from 5 to 90% of 1,3,3,3-tetrafluoropropene.

According to another embodiment of said process for reducingenvironmental impact, the initial heat-transfer fluid isdifluoromethane, and the final heat-transfer fluid comprises:

-   -   from 2 to 30% of 2,3,3,3-tetrafluoropropene, from 68 to 96% of        difluoromethane and from 2 to 20% of 3,3,3-trifluoropropene,        ideally from 8 to 23% of 2,3,3,3-tetrafluoropropene, from 75 to        90% of difluoromethane and from 2 to 10% of        3,3,3-trifluoropropene; or    -   from 2 to 40% of 2,3,3,3-tetrafluoropropene, from 58 to 90% of        difluoromethane and from 2 to 40% of 3,3,3-trifluoropropene,        ideally from 2 to 23% of 2,3,3,3-tetrafluoropropene, from 75 to        90% of difluoromethane and from 2 to 18% of        3,3,3-trifluoropropene.

The present invention makes it possible to overcome the drawbacks of theprior art. It provides more particularly heat-transfer fluids that havea relatively low GWP and that have good energy performance levels, inparticular in applications using countercurrent heat exchangers.

This is accomplished by virtue of ternary mixtures comprising HFO-1243zfand HFC-32, the rest making up the mixtures being selected fromHFO-152a, HFO-1234yf and HFO-1234ze. These three compounds arehydrocarbon-based molecules which have at least two fluorinesubstituents and a boiling point of between −30° C. and −18° C. HFC-152ahas a boiling point of −24° C., HFO-1234yf has a boiling point of −29°C. and HFO-trans-1234ze has a boiling point of −19° C.

The ternary mixtures above have the particularity of exhibiting goodenergy performance levels, in particular with countercurrent heatexchangers.

According to some particular embodiments, the invention also has one orpreferably more of the advantageous characteristics listed below.

-   -   The heat-transfer fluids of the invention have a coefficient of        performance which is higher than the reference refrigerants        R404a, R407c, HFC-134a, HFC-32 and R410a in applications        involving a countercurrent heat exchanger. In certain cases, the        capacity of the heat-transfer fluids is greater than or equal to        that of the reference refrigerants, in these same applications.        Correspondingly, the invention makes it possible to reduce the        GWP of existing systems comprising one of the above reference        refrigerants, without being detrimental to the performance        levels of these systems, and, on the contrary, while improving        them to a large extent, by replacing the reference refrigerants        with the heat-transfer fluids of the invention.    -   The heat-transfer fluids of the invention have a coefficient of        performance which is higher than that of the        HFO-1243zf/HFC-134a/HFC-32 mixture such as is used in document        US 2009/0158771.    -   The heat-transfer fluids of the invention are less inflammable        and/or more effective than those used in document WO        2009/150763.

According to the invention, the global warming potential (GWP) isdefined relative to carbon dioxide and with respect to a period of 100years, according to the method indicated in “The scientific assessmentof ozone depletion, 2002, a report of the World MeteorologicalAssociation's Global Ozone Research and Monitoring Project”.

DESCRIPTION OF EMBODIMENTS OF THE INVENTION

The invention is now described in greater detail and in a non-limitingmanner in the description which follows.

The term “heat-transfer compound”, respectively “heat-transfer fluid”(or refrigerant fluid) is intended to mean a compound, respectively afluid, capable of absorbing heat by evaporating at low temperature andlow pressure and of releasing heat by condensing at high temperature andhigh pressure, in a vapor compression circuit. Generally, aheat-transfer fluid may comprise just one, or two, three or more thanthree heat-transfer compounds.

The term “heat-transfer composition” is intended to mean a compositioncomprising a heat-transfer fluid and, optionally, one or more additiveswhich are not heat-transfer compounds for the envisioned application.

The heat transfer process according to the invention is based on the useof equipment comprising a vapor compression circuit which contains aheat-transfer fluid. The heat-transfer process may be a process forheating or cooling a fluid or body.

The vapor compression circuit containing a heat-transfer fluid comprisesat least one evaporator, a compressor, a condenser and an expansionvalve, and also is for transporting heat-transfer fluid between thesecomponents. The evaporator and the condenser comprise a heat exchangermaking it possible to exchange heat between the heat-transfer fluid andanother fluid or body.

By way of compressor, use may in particular be made of a centrifugalcompressor having one or more stages or a centrifugal mini-compressor.Rotary compressors, reciprocating compressors or screw compressors canalso be used. The compressor may be driven by an electric motor or by agas turbine (for example fed with the exhaust gases of a vehicle, formobile applications), or by gearing.

The equipment may comprise a turbine for generating electricity (Rankinecycle).

The equipment may also optionally comprise at least one coolant circuitused for transmitting heat (with or without a change of state) betweenthe heat-transfer fluid circuit and the fluid or body to be heated orcooled.

The equipment may also optionally comprise two (or more) vaporcompression circuits containing identical or distinct heat-transferfluids. For example, the vapor compression circuits may be coupledtogether.

The vapor compression circuit operates according to a conventional vaporcompression cycle. The cycle comprises the change of state of theheat-transfer fluid from a liquid phase (or liquid/vapor two phasestate) to a vapor phase at a relatively low pressure, then thecompression of the fluid in the vapor phase up to a relatively highpressure, the change of state (condensation) of the heat-transfer fluidfrom the vapor phase to the liquid phase at a relatively high pressure,and the reduction of the pressure in order to recommence the cycle.

In the case of a cooling process, heat from the fluid or from the bodythat is being cooled (directly or indirectly, via a coolant) is absorbedby the heat-transfer fluid, during the evaporation of the latter, at arelatively low temperature compared with the surroundings. The coolingprocesses include air-conditioning processes (with mobile equipment, forexample in vehicles, or stationary equipment), refrigeration processesand freezing processes or cryogenic processes.

In the case of a heating process, heat is imparted (directly orindirectly, via a coolant) from the heat-transfer fluid, during thecondensation thereof, to the fluid or the body that is being heated, ata relatively high temperature compared to the surroundings. Theequipment that makes it possible to implement the heat transfer iscalled, in this case, a “heat pump”.

It is possible to use any type of heat exchanger for using theheat-transfer fluids according to the invention, and in particularcocurrent heat exchangers.

However, according to a preferred embodiment, the invention provides forthe cooling and heating processes, and the corresponding equipment, tocomprise a countercurrent heat exchanger, said heat exchanger beingcountercurrent with respect either to the condenser or to theevaporator. Indeed, the heat-transfer fluids according to the inventionare particularly effective with countercurrent heat exchangers.Preferably, both the evaporator and the condenser comprise acountercurrent heat exchanger.

According to the invention, the term “countercurrent heat exchanger” isintended to mean a heat exchanger in which the heat is exchanged betweena first fluid and a second fluid, the first fluid at the inlet of theexchanger exchanging heat with the second fluid at the outlet of theexchanger, and the first fluid at the outlet of the exchanger exchangingheat with the second fluid at the inlet of the exchanger.

For example, the countercurrent heat exchangers include devices in whichthe flow of the first fluid and the flow of the second fluid are inopposite directions or virtually opposite directions. Exchangers whichoperate in cross-current mode with countercurrent tendency are alsoincluded among the countercurrent heat exchangers within the meaning ofthe present application.

The meaning of the various abbreviations used to denote the variouschemical compounds mentioned in the application is the following:

-   -   HFC-134a:1,1,1,2-tetrafluoroethane;    -   HFC-143a:1,1,1-trifluoroethane;    -   HFC-125: pentafluoroethane;    -   HFC-32: difluoromethane;    -   HFC-152a:1,1-difluoroethane;    -   HFC-41: fluoromethane;    -   HFO-1234ze: 1,3,3,3-tetrafluoropropene;    -   HFO-1234yf: 2,3,3,3-tetrafluoropropene;    -   HFO-1243g: 3,3,3-trifluoropropene.

The heat-transfer fluids used in the invention are the following ternarymixtures:

-   -   1) HFC-32, HFC-152a and HFO-1243zf;    -   2) HFO-1234yf, HFC-32 and HFO-1243zf; and    -   3) HFC-32, HFO-1243zf and HFO-1234ze.

Compositions 2) and 3) have the advantage of being less inflammable thanthose described in document WO 2009/150763.

The term “ternary mixture” is intended to mean a composition consistingessentially of the three compounds mentioned, i.e. in which the threecompounds mentioned represent at least 99% (preferably at least 99.5% oreven at least 99.9%) of the composition.

Unless otherwise mentioned, throughout the application, the proportionsof compounds indicated are given as percentages by weight.

The HFO-1234ze may be in cis or trans form or be a mixture of these twoforms.

In each of the three compositions above, each compound can be presentpreferably in an amount of from 1 to 99%, and in particular from 1 to96%.

For use in low-temperature refrigeration processes, i.e. those in whichthe temperature of the fluid or of the body cooled is from −40° C. to−10° C., and preferably from −35° C. to −25° C., more particularlypreferably from −30° C. to −20° C. (ideally approximately −25° C.), ithas been found that the compounds which are most effective as areplacement for R404a or R407c are the following:

-   -   for composition 1): from 20 to 70% of HFC-32, from 2 to 30% of        HFC-152a and from 2 to 78% of HFO-1243zf, and preferably from 25        to 65% of HFC-32, from 2 to 15% of HFC-152a and from 20 to 78%        of HFO-1243zf;    -   for composition 2): from 5 to 70% of HFO-1234yf, from 20 to 60%        of HFC-32 and from 2 to 75% of HFO-1243zf, and preferably from        10 to 70% of HFO-1234yf, from 25 to 50% of HFC-32 and from 2 to        65% of HFO-1243zf; and    -   for composition 3): from 25 to 70% of HFC-32, from 2 to 70% of        HFO-1243zf and from 5 to 73% of HFO-1234ze, and preferably from        25 to 50% of HFC-32, from 5 to 70% of HFO-1243zf and from 5 to        55% of HFO-1234ze.

For use in low-temperature refrigeration processes, i.e. those in whichthe temperature of the fluid or of the body cooled is from −40° C. to−10° C., and preferably from −35° C. to −25° C., more particularlypreferably from −30° C. to −20° C. (ideally approximately −25° C.), ithas been found that the compositions which are most effective as areplacement for R410a are the following:

-   -   for composition 1): from 60 to 96% of HFC-32, from 2 to 20% of        HFC-152a and from 2 to 20% of HFO-1243zf, and preferably from 80        to 90% of HFC-32, from 5 to 15% of HFC-152a and from 5 to 15% of        HFO-1243zf;    -   for composition 2): from 2 to 40% of HFO-1234yf, from 58 to 90%        of HFC-32 and from 2 to 40% of HFO-1243zf, and preferably from 5        to 30% of HFO-1234yf, from 65 to 80% of HFC-32 and from 2 to 15%        of HFO-1243zf; and    -   for composition 3): from 50 to 96% of HFC-32, from 2 to 50% of        HFO-1243zf and from 2 to 50% of HFO-1234ze, and preferably from        65 to 90% of HFC-32, from 5 to 30% of HFO-1243zf and from 5 to        30% of HFO-1234ze.

For use in:

-   -   moderate-temperature cooling processes, i.e. those in which the        temperature of the fluid or the body cooled is from −15° C. to        15° C., preferably from −10° C. to 10° C., more particularly        preferably from −5° C. to 5° C. (ideally approximately 0° C.),        and also    -   moderate-temperature heating processes, i.e. those in which the        temperature of the fluid or of the body heated is from 30° C. to        80° C., and preferably from 35° C. to 55° C., more particularly        preferably from 40° C. to 50° C. (ideally approximately 45° C.),        it has been found that the compositions which are most effective        as a replacement for HFC-134a are the following:    -   for composition 1): from 2 to 20% of HFC-32, from 2 to 85% of        HFC-152a and from 2 to 90% of HFO-1243zf, and preferably from 5        to 15% of HFC-32, from 5 to 85% of HFC-152a and from 10 to 90%        of HFO-1243zf;    -   for composition 2): from 5 to 75% of HFO-1234yf, from 2 to 20%        of HFC-32 and from 2 to 90% of HFO-1243zf, and preferably from 5        to 75% of HFO-1234yf, from 5 to 15% of HFC-32 and from 10 to 90%        of HFO-1243zf; and    -   for composition 3): from 2 to 25% of HFC-32, from 2 to 90% of        HFO-1243zf and from 5 to 96% of HFO-1234ze, and preferably from        5 to 25% of HFC-32, from 5 to 90% of HFO-1243zf and from 5 to        90% of HFO-1234ze.

For use in:

-   -   moderate-temperature cooling processes, i.e. those in which the        temperature of the fluid or of the body cooled is from −15° C.        to 15° C., preferably from −10° C. to 10° C., more particularly        preferably from −5° C. to 5° C. (ideally approximately 0° C.),        and also    -   moderate-temperature heating processes, i.e. those in which the        temperature of the fluid or of the body heated is from 30° C. to        80° C., and preferably from 35° C. to 55° C., more particularly        preferably from 40° C. to 50° C. (ideally approximately 45° C.),        it has been found that the compositions which are most effective        as a replacement for R404a or for R407c are the following:    -   for composition 1): from 20 to 60% of HFC-32, from 2 to 70% of        HFC-152a and from 2 to 70% of HFO-1243zf, and preferably from 25        to 40% of HFC-32, from 5 to 65% of HFC-152a and from 5 to 70% of        HFO-1243zf;    -   for composition 2): from 5 to 80% of HFO-1234yf, from 20 to 50%        of HFC-32 and from 2 to 75% of HFO-1243zf, and preferably from 5        to 65% of HFO-1234yf, from 25 to 35% of HFC-32 and from 2 to 70%        of HFO-1243zf; and    -   for composition 3): from 20 to 65% of HFC-32, from 2 to 70% of        HFO-1243zf and from 5 to 78% of HFO-1234ze, and preferably from        25 to 50% of HFC-32, from 5 to 70% of HFO-1243zf and from 5 to        70% of HFO-1234ze.

For use in:

-   -   moderate-temperature cooling processes, i.e. those in which the        temperature of the fluid or of the body cooled is from −15° C.        to 15° C., preferably from −10° C. to 10° C., more particularly        preferably from −5° C. to 5° C. (ideally about 0° C.), and also    -   moderate-temperature heating processes, i.e. those in which the        temperature of the fluid or of the body heated is from 30° C. to        80° C., and preferably from 35° C. to 55° C., more particularly        preferably from 40° C. to 50° C. (ideally approximately 45° C.),        it has been found that the compositions which are most effective        as a replacement for R410a are the following:    -   for composition 1): from 50 to 96% of HFC-32, from 2 to 30% of        HFC-152a and from 2 to 30% of HFO-1243zf, and preferably from 65        to 80% of HFC-32, from 5 to 25% of HFC-152a and from 5 to 30% of        HFO-1243zf;    -   from composition 2): from 2 to 30% of HFO-1234yf, from 60 to 90%        of HFC-32 and from 2 to 30% of HFO-1243zf, and preferably from 5        to 25% of HFO-1234yf, from 65 to 80% of HFC-32 and from 5 to 30%        of HFO-1243zf; and    -   for composition 3): from 50 to 96% of HFC-32, from 2 to 48% of        HFO-1243zf and from 2 to 30% of HFO-1234ze, and preferably from        65 to 90% of HFC-32, from 5 to 30% of HFO-1243zf and from 5 to        30% of HFO-1234ze.

For use in low-temperature refrigeration processes, i.e. those in whichthe temperature of the fluid or of the body cooled is from −40° C. to−10° C., and preferably from −35° C. to −25° C., more particularlypreferably from −30° C. to −20° C. (ideally approximately −25° C.), ithas been found that the compositions which are most effective as areplacement for HFC-32 are the following:

-   -   for composition 2): from 2 to 30% of HFO-1234yf, from 68 to 96%        of HFC-32 and from 2 to 20% of HFO-1243zf, and preferably from 8        to 23% of HFO-1234yf, from 75 to 90% of HFC-32 and from 2 to 10%        of HFO-1243zf.

For use in:

-   -   moderate-temperature cooling processes, i.e. those in which the        temperature of the fluid or of the body cooled is from −15° C.        to 15° C., preferably from −10° C. to 10° C., more particularly        preferably from −5° C. to 5° C. (ideally approximately 0° C.),        and also    -   moderate-temperature heating processes, i.e. those in which the        temperature of the fluid or of the body heated is from 30° C. to        80° C., and preferably from 35° C. to 55° C., more particularly        preferably from 40° C. to 50° C. (ideally approximately 45° C.),        it has been found that the compositions which are most effective        as a replacement for HFC-32 are the following:    -   for composition 2): from 2 to 40% of HFO-1234yf, from 58 to 90%        of HFC-32 and from 2 to 40% of HFO-1243zf, and preferably from 2        to 23% of HFO-1234yf, from 75 to 90% of HFC-32 and from 2 to 18%        of HFO-1243zf.

The above compositions used to replace HFC-32 have the advantage notonly of an improved performance level, but also of a lower temperatureat the outlet of the compressor, thereby reducing the heat losses,facilitating the compression and reducing the compressive mechanicalstrains.

In the “low-temperature refrigeration” processes mentioned above, theinlet temperature of the heat-transfer fluid at the evaporator ispreferably from −45° C. to −15° C., in particular from −40° C. to −20°C., more particularly preferably from −35° C. to −25° C. and, forexample, approximately −30° C.; and the temperature at the beginning ofthe condensation of the heat-transfer fluid at the condenser ispreferably from 25° C. to 80° C., in particular from 30° C. to 60° C.,more particularly preferably from 35° C. to 55° C. and, for example,approximately 40° C.

In the “moderate-temperature refrigeration” processes mentioned above,the inlet temperature of the heat-transfer fluid at the evaporator ispreferably from −20° C. to 10° C., in particular from −15° C. to 5° C.,more particularly preferably from −10° C. to 0° C. and, for example,approximately −5° C.; and the temperature at the beginning of thecondensation of the heat-transfer fluid at the condenser is preferablyfrom 25° C. to 80° C., in particular from 30° C. to 60° C., moreparticularly preferably from 35° C. to 55° C. and, for example,approximately 50° C. These processes may be refrigeration orair-conditioning processes.

In the “moderate-temperature heating” processes mentioned above, theinlet temperature of the heat-transfer fluid at the evaporator ispreferably from −20° C. to 10° C., in particular from −15° C. to 5° C.,more particularly preferably from −10° C. to 0° C. and, for example,approximately −5° C.; and the temperature at the beginning of thecondensation of the heat-transfer fluid at the condenser is preferablyfrom 25° C. to 80° C., in particular from 30° C. to 60° C., moreparticularly preferably from 35° C. to 55° C. and, for example,approximately 50° C.

In addition, the mixtures having the following formulations arequasi-azeotropic mixtures:

-   -   from 75 to 98% of HFC-32, from 1 to 9% of HFC-152a and from 1 to        23% of HFO-1243zf;    -   from 1 to 28% of HFO-1234yf, from 70 to 98% of HFC-32 and from 1        to 23% of HFO-1243zf;    -   from 75 to 98% of HFC-32, from 1 to 23% of HFO-1243zf and from 1        to 10% of HFO-1234ze.

For these heat-transfer fluids, at constant temperature, the liquidsaturation pressure and the vapor saturation pressure are virtuallyidentical (the maximum pressure difference being 10%). Theseheat-transfer fluids have an advantage in terms of ease of use. In theabsence of significant temperature glide, there is no significant changein the composition circulating, and no significant change either in thecomposition in the event of a leak. These heat-transfer fluids areparticularly suitable for replacing R410a, for example.

The heat-transfer fluids which are not quasi-azeotropic, for their part,are however very effective when they are correctly coupled with acountercurrent heat exchanger (with a temperature difference with thesecond fluid which is approximately constant in the exchanger).

Each heat-transfer fluid above can be mixed with one or more additivesso as to provide the heat transfer composition actually circulating inthe vapor compression circuit. The additives can in particular beselected from lubricants, stabilizers, surfactants, tracers, fluorescentagents, odorous agents, solubilizing agents and mixtures thereof.

When it (they) is (are) present, the stabilizer(s) preferablyrepresent(s) at most 5% by weight in the heat-transfer composition.Among the stabilizers, mention may in particular be made ofnitromethane, ascorbic acid, terephthalic acid, azoles such astolutriazole or benzotriazole, phenolic compounds such as tocopherol,hydroquinone, t-butyl hydroquinone, 2,6-di-tert-butyl-4-methylphenol,epoxides (alkyl, optionally fluorinated or perfluorinated, or alkenyl oraromatic) such as n-butyl glycidyl ether, hexanediol diglycidyl ether,allyl diglycidyl ether, butylphenyl glycidyl ether, phosphites,phosphonates, thiols and lactones.

By way of lubricants, use may in particular be made of oils of mineralorigin, silicone oils, paraffins, naphthenes, synthetic paraffins,alkylbenzenes, poly-α-olefins, polyalkene glycols, polyol esters and/orpolyvinyl ethers.

By way of tracers (capable of being detected), mention may be made ofhydrofluorocarbons, deuterated hydrofluorocarbons, deuteratedhydrocarbons, perfluorocarbons, fluoroethers, brominated compounds,iodinated compounds, alcohols, aldehydes, ketones, nitrous oxide andcombinations thereof. The tracer is different than the heat-transfercompound(s) making up the heat-transfer fluid.

By way of solubilizing agents, mention may be made of hydrocarbons,dimethyl ether, polyoxyalkylene ethers, amides, ketones, nitriles,chlorocarbons, esters, lactones, aryl ethers, fluoroethers and1,1,1-trifluoroalkanes. The solubilizing agent is different than theheat-transfer compound(s) making up the heat-transfer fluid.

By way of fluorescent agents, mention may be made of naphthalimides,perylenes, coumarins, anthracenes, phenanthracenes, xanthenes,thioxanthenes, naphthoxanthenes, fluoresceins and derivatives andcombinations thereof.

By way of odorous agents, mention may be made of alkyl acrylates, allylacrylates, acrylic acids, acryl esters, alkyl ethers, alkyl esters,alkynes, aldehydes, thiols, thioethers, disulfides, allylisothiocyanates, alkanoic acids, amines, norbornenes, norbornenederivatives, cyclohexene, aromatic heterocyclic compounds, ascaridole,o-methoxy(methyl)phenol and combinations thereof.

The compositions according to the invention can also be used as anexpansion agent, an aerosol or a solvent.

EXAMPLES

The following examples illustrate the invention without limiting it.

Example 1: Method for Calculating the Properties of the Heat-TransferFluids in the Various Configurations Envisioned

The RK-Soave equation is used for the calculation of the densities,enthalpies, entropies and liquid/vapor equilibrium data of the mixtures.The use of this equation requires knowledge of the properties of thepure substances used in the mixtures in question and also theinteraction coefficients for each binary mixture.

The data necessary for each pure substance are the boiling point, thecritical temperature and the critical pressure, the pressure curve as afunction of the temperature from the boiling point up to the criticalpoint, and the saturated liquid and saturated vapor densities as afunction of the temperature.

The data with regard to HFCs are published in the ASHRAE Handbook 2005,chapter 20, and are also available under Refprop (software developed byNIST for the calculation of the properties of refrigerant fluids).

The HFO temperature-pressure curve data are measured by the staticmethod. The critical temperature and the critical pressure are measuredusing a C80 calorimeter sold by Setaram. The densities, at saturation asa function of the temperature, are measured by means of thevibrating-tube densimeter technology developed by the laboratories ofthe école de Mines de Paris [French Engineering School].

The RK-Soave equation uses coefficients of binary interaction torepresent the behavior of products in mixtures. The coefficients arecalculated according to the experimental liquid/vapor equilibrium data.

The technique used for the liquid/vapor equilibrium measurements is thestatic analytical cell method. The equilibrium cell comprises a sapphiretube and is equipped with two Rolsitm electromagnetic samplers. It isimmersed in a cryothermostat bath (Huber HS40). Magnetic stirring drivenby a magnetic field rotating at a variable speed is used to acceleratethe reaching of the equilibria. The sample analysis is carried out bygas chromatography (HP5890 series II) using a katharometer (TCD).

Liquid/vapor equilibrium measurements on the binary mixtureHFC-32/HFO-1234ze are carried out for the following isotherm: 15° C.

The liquid/vapor equilibrium measurements on the binary mixtureHFC-32/HFO-1234yf are carried out for the following isotherms: 70° C.,30° C., −10° C.

The liquid/vapor equilibrium data for the binary HFC-152a/HFO-32 areavailable under Refprop. Two isotherms (−20° C. and 20° C.) and twoisobars (1 bar and 25 bar) are used for the calculation of theinteraction coefficients for this binary mixture.

The liquid/vapor equilibrium measurements on the binary mixtureHFC-32/HFO-1243zf are carried out for the following isotherms: −15° C.and 0° C.

The liquid/vapor equilibrium measurements on the binary mixtureHFO-1234yf/HFO-1243zf are carried out for the following isotherm: 21.3°C.

A compression system equipped with a countercurrent evaporator andcondenser, with a screw compressor and with an expansion valve isconsidered.

The system operates with 15° C. of overheat and 5° C. of undercooling.The minimum temperature difference between the secondary fluid and therefrigerant fluid is considered to be about 5° C.

The isentropic efficiency of the compressors depends on the compressionratio. This efficiency is calculated according to the followingequation:

$\begin{matrix}{\eta_{isen} = {a - {b\left( {\tau - c} \right)}^{2} - \frac{d}{\tau - e}}} & (1)\end{matrix}$

For a screw compressor, the constants a, b, c, d and e of the isentropicefficiency equation (1) are calculated according to the standard datapublished in the “Handbook of air conditioning and refrigeration”, page11.52.

The coefficient of performance (COP) is defined as being the usefulpower supplied by the system over the power provided or consumed by thesystem.

The Lorenz coefficient of performance (COPLorenz) is a referencecoefficient of performance. It depends on temperatures and is used tocompare the COPs of the various fluids.

The Lorenz coefficient of performance is defined as follows (thetemperatures T are in K):T _(average) ^(condenser) =T _(inlet) ^(condenser) −T _(outlet)^(condenser)  (2)T _(average) ^(evaporator) =T _(outlet) ^(evaporator) −T _(inlet)^(evaporator)  (3)

The Lorenz COP in the case of conditioned air and of refrigeration is:

$\begin{matrix}{{COPlorenz} = \frac{T_{average}^{evaporator}}{T_{average}^{condenser} - T_{average}^{evaporator}}} & (4)\end{matrix}$

The Lorenz COP in the case of heating is:

$\begin{matrix}{{COPlorenz} = \frac{T_{average}^{condenser}}{T_{average}^{condenser} - T_{average}^{evaporator}}} & (5)\end{matrix}$

For each composition, the coefficient of performance of the Lorenz cycleis calculated as a function of the corresponding temperatures.

In low-temperature refrigeration mode, the compression system operatesbetween an inlet temperature of the refrigerant fluid at the evaporatorof −30° C. and a temperature at the beginning of the condensation of therefrigerant fluid at the condenser of 40° C. The system providesrefrigeration at −25° C.

In moderate-temperature heating mode, the compression system operatesbetween an inlet temperature of the refrigerant fluid at the evaporatorof −5° C. and a temperature at the beginning of the condensation of therefrigerant fluid at the condenser of 50° C. The system supplies heat at45° C.

In moderate-temperature cooling mode, the compression system operatesbetween an inlet temperature of the refrigerant fluid at the evaporatorof −5° C. and a temperature at the beginning of the condensation of therefrigerant fluid at the condenser of 50° C. The system providesrefrigeration at 0° C.

In the tables that follow, “Temp. evap outlet” denotes the temperatureof the fluid at the outlet of the evaporator, “Temp. comp outlet”denotes the temperature of the fluid at the outlet of the compressor, “Tcond outlet” denotes the temperature of the fluid at the outlet of thecondenser, “evap P” denotes the pressure of the fluid in the evaporator,“cond P” denotes the pressure of the fluid in the condenser, “Ratio(w/w)” denotes the compression ratio, “Glide” denotes the temperatureglide, “comp efficiency” denotes the efficiency of the compressor, “%CAP” denotes the volumetric capacity of the fluid relative to thereference fluid indicated on the first line, “% COP/COPLorenz” denotesthe ratio of the COP of the system relative to the COP of thecorresponding Lorenz cycle, “Psat liquid” denotes the liquid saturationpressure, “Psat vapor” denotes the vapor saturation pressure, and “%diff in pressure” denotes the difference between these two pressures,expressed as a percentage.

Example 2: Results for a Low-Temperature Refrigeration, Comparison withR404a and R407c

HFC-32/HFC-152a/HFO-1243zf mixture:

Temp evap Temp comp T cond evap P cond P Ratio comp % COP/ Composition(%) outlet (° C.) outlet (° C.) outlet (° C.) (bar) (bar) (w/w) Glideefficiency % CAP COPLorenz R404A −30 101 40 2.1 18.1 8.8 0.46 53.8 10032 R407C −26 131 35 1.7 15.3 9.0 4.48 51.9 108 35 HFC-32 HFC-152aHFO-1243zf 25 10 65 −25 122 31 1.4 12.4 8.6 4.96 55.1 95 38 35 30 35 −25151 31 1.5 13.8 9.1 5.03 51.5 106 36 35 20 45 −25 140 31 1.6 14.0 8.85.25 54.1 108 38 35 10 55 −24 128 31 1.7 14.1 8.4 5.57 57.1 111 40 50 2525 −25 164 33 1.8 16.3 8.9 5.35 52.5 125 36 50 15 35 −25 152 33 1.9 16.68.6 5.24 54.9 127 38 50 5 45 −25 139 33 2.0 16.9 8.3 5.19 57.8 131 40 6510 25 −26 171 36 2.2 19.4 8.8 4.22 53.6 143 36

HFO-1234yf/HFC-32/HFO-1243zf mixture:

Temp evap Temp comp T cond evap P comp % COP/ Composition (%) outlet (°C.) outlet (° C.) outlet (° C.) (bar) cond P (bar) Ratio (w/w) Glideefficiency % CAP COPLorenz R404A −30 101 40 2.1 18.1 8.8 0.46 53.8 10032 R407C −26 131 35 1.7 15.3 9.0 4.48 51.9 108 35 HFO- HFC- HFO- 1234yf32 1243zf 70 25 5 −25 103 32 1.8 14.7 8.1 5.20 59.2 109 40 60 25 15 −25104 32 1.8 14.4 8.1 5.33 59.1 108 40 50 25 25 −25 105 31 1.7 14.0 8.15.49 59.2 108 41 40 25 35 −24 105 31 1.7 13.7 8.1 5.62 59.4 107 41 30 2545 −24 106 31 1.7 13.3 8.1 5.68 59.4 105 42 20 25 55 −24 107 30 1.6 13.08.1 5.65 59.3 103 42 10 25 65 −24 108 30 1.6 12.7 8.1 5.56 59.0 100 4160 35 5 −25 112 34 2.1 16.6 8.1 4.98 59.6 123 40 50 35 15 −25 114 33 2.016.3 8.1 5.24 59.6 123 41 40 35 25 −24 114 32 2.0 15.8 8.0 5.50 59.9 12241 30 35 35 −24 114 32 1.9 15.4 8.0 5.71 60.2 121 42 20 35 45 −24 114 311.9 14.9 7.9 5.85 60.5 119 42 10 35 55 −24 115 31 1.8 14.5 7.9 5.90 60.5117 42 45 50 5 −26 132 36 2.3 19.4 8.3 3.54 57.8 139 38 35 50 15 −26 13435 2.3 18.9 8.3 3.96 57.8 138 39 25 50 25 −26 134 35 2.2 18.4 8.2 4.3558.2 137 39 15 50 35 −25 133 34 2.2 17.8 8.2 4.67 58.6 136 40 5 50 45−25 133 33 2.1 17.2 8.1 4.92 59.2 134 41

HFC-32/HFO-1243zf/HFO-1234ze mixture:

Temp evap Temp comp T cond evap P cond P comp % COP/ Composition (%)outlet (° C.) outlet (° C.) outlet (° C.) (bar) (bar) Ratio (w/w) Glideefficiency % CAP COPLorenz R404A −30 101 40 2.1 18.1 8.8 0.46 53.8 10032 R407C −26 131 35 1.7 15.3 9.0 4.48 51.9 108 35 HFO- HFO- HFC-321243zf 1234ze 25 70 5 −24 111 30 1.5 12.4 8.2 5.58 58.2 97 41 25 60 15−24 112 30 1.5 12.3 8.3 5.86 57.5 97 41 25 50 25 −24 113 31 1.5 12.2 8.46.09 57.1 96 40 35 60 5 −24 117 30 1.8 14.1 8.0 6.03 60.1 114 42 35 5015 −24 118 31 1.7 14.0 8.0 6.34 59.7 113 42 35 40 25 −23 117 31 1.7 13.78.0 6.64 59.7 112 42 35 30 35 −23 117 30 1.7 13.5 8.0 6.95 59.8 111 4235 20 45 −23 118 30 1.7 13.3 8.1 7.28 59.6 110 42 35 10 55 −22 119 311.6 13.2 8.1 7.66 59.1 109 42 50 45 5 −25 133 33 2.1 16.9 8.1 5.26 59.2133 41 50 35 15 −24 132 32 2.1 16.5 8.0 5.77 59.7 133 42 50 25 25 −24131 32 2.0 16.1 8.0 6.28 60.4 132 42 50 15 35 −23 130 31 2.0 15.8 7.96.78 60.7 132 43 50 5 45 −23 132 32 2.0 15.8 8.0 7.23 60.3 131 42

Example 3: Results for a Low-Temperature Refrigeration, Comparison withR410a

HFC-32/HFC-152a/HFO-1243zf mixture:

Temp evap Temp comp T cond evap P comp % COP/ Composition (%) outlet (°C.) outlet (° C.) outlet (° C.) (bar) cond P (bar) Ratio (w/w) Glideefficiency % CAP COPLorenz R410A −30 153 40 2.7 24.2 8.9 0.06 52.5 10033 HFC- HFO- HFC-32 152a 1243zf 80 15 5 −26 202 38 2.3 21.4 9.1 3.9950.8 102 34 80 5 15 −27 192 38 2.5 22.2 9.0 2.52 52.1 103 34 90 5 5 −28207 39 2.6 23.4 9.1 1.88 51.4 108 34

HFO-1234yf/HFC-32/HFO-1243zf mixture:

Temp evap Temp comp T cond evap P cond P comp % COP/ Composition (%)outlet (° C.) outlet (° C.) outlet (° C.) (bar) (bar) Ratio (w/w) Glideefficiency % CAP COPLorenz R410A −30 153 40 2.7 24.2 8.9 0.06 52.5 10033 HFO- HFO- 1234yf HFC-32 1243zf 30 65 5 −28 156 38 2.5 21.6 8.6 1.8755.4 99 37 20 65 15 −28 158 37 2.5 21.2 8.6 2.37 55.2 98 36 15 80 5 −29182 39 2.6 23.3 8.8 0.71 53.3 106 35  5 80 15 −29 185 39 2.6 22.9 8.91.25 52.8 104 35

HFC-32/HFO-1243zf/HFO-1234ze mixture:

Temp evap Temp comp T cond evap P cond P comp % COP/ Composition (%)outlet (° C.) outlet (° C.) outlet (° C.) (bar) (bar) Ratio (w/w) Glideefficiency % CAP COPLorenz R410A −30 153 40 2.7 24.2 8.9 0.06 52.5 10033 HFO- HFO- HFC-32 1243zf 1234ze 65 30 5 −26 156 35 2.3 19.7 8.5 3.7056.5 97 38 65 20 15 −26 153 35 2.3 19.1 8.3 4.50 57.9 97 40 65 10 25 −25151 34 2.3 18.6 6.2 5.21 58.8 97 41 80 15 5 −28 183 38 2.5 22.2 8.8 2.0653.8 104 36 80 5 15 −27 178 37 2.5 21.5 8.6 2.99 55.3 105 37 90 5 5 −29199 39 2.6 23.5 8.9 1.12 52.6 109 35

Example 4: Results for a Moderate-Temperature Cooling, Comparison withHFC-134a

HFC-32/HFC-152a/HFO-1243zf mixture:

Temp evap Temp comp T cond evap P cond P comp % COP/ Composition (%)outlet (° C.) outlet (° C.) outlet (° C.) (bar) (bar) Ratio (w/w) Glideefficiency % CAP COPLorenz R134a −5 81 50 2.4 13.2 5.4 0.00 75.9 100 54HFO- HFC-32 HFC-152a 1243zf 5 5 90 −3 75 47 2.6 12.3 4.7 1.82 78.9 10457 5 15 80 −3 78 47 2.6 12.5 4.8 1.65 78.5 106 57 5 25 70 −3 81 47 2.612.6 4.9 1.54 78.2 107 57 5 35 60 −4 84 47 2.6 12.7 4.9 1.46 78.0 109 585 45 50 −4 86 47 2.6 12.7 5.0 1.38 77.7 110 58 5 55 40 −4 89 48 2.5 12.75.0 1.31 77.6 110 58 5 65 30 −4 91 48 2.5 12.7 5.1 1.22 77.4 110 58 5 7520 −4 93 48 2.5 12.6 5.1 1.11 77.2 110 58 5 85 10 −4 95 48 2.4 12.5 5.20.97 76.9 109 58 15 5 80 0 79 42 3.3 14.0 4.2 4.79 80.4 135 59 15 15 70−1 82 43 3.3 14.1 4.3 4.31 80.0 135 58 15 25 60 −1 85 43 3.2 14.2 4.44.02 79.7 135 59 15 35 50 −1 87 44 3.1 14.2 4.5 3.81 79.4 135 59 15 4540 −1 90 44 3.1 14.2 4.6 3.64 79.2 136 59 15 55 30 −2 93 44 3.0 14.1 4.73.47 78.9 135 60 15 65 20 −2 95 44 2.9 14.0 4.8 3.27 78.6 134 60 15 7510 −2 98 44 2.8 13.8 4.9 3.02 78.3 133 60

HFO-1234yf/HFC-32/HFO-1243zf mixture:

Temp evap Temp comp T cond evap P cond P comp % COP/ Composition (%)outlet (° C.) outlet (° C.) outlet (° C.) (bar) (bar) Ratio (w/w) Glideefficiency % CAP COPLorenz R134a −5 81 50 2.4 13.2 5.4 0.00 75.9 100 54HFO- HFO 1234yf HFC-32 1243zf 5 5 90 −3 73 46 2.6 12.2 4.6 1.93 79.1 10457 15 5 80 −3 72 46 2.7 12.4 4.6 1.92 79.2 105 57 25 5 70 −3 72 46 2.712.6 4.6 1.92 79.2 106 56 35 5 60 −3 72 46 2.8 12.8 4.6 1.94 79.2 107 5645 5 50 −3 71 46 2.8 13.0 4.6 1.97 79.2 108 56 55 5 40 −3 71 46 2.9 13.24.6 1.99 79.2 109 55 65 5 30 −3 71 46 2.9 13.5 4.6 2.00 79.2 110 55 5 1580 0 77 42 3.4 14.0 4.1 5.12 80.7 137 59 15 15 70 0 76 42 3.5 14.3 4.15.07 80.7 139 59 25 15 60 0 76 42 3.6 14.6 4.1 5.07 80.7 141 59 35 15 500 76 42 3.6 14.9 4.1 5.08 80.7 143 58 45 15 40 0 76 42 3.7 15.2 4.1 5.0780.6 145 58 55 15 30 0 75 42 3.8 15.6 4.1 5.02 80.6 146 57 65 15 20 0 7542 3.8 15.9 4.1 4.93 80.6 147 57 75 15 10 0 75 43 3.9 16.2 4.1 4.82 80.6148 56

HFC-32/HFO-1243zf/HFO-1234ze mixture:

Temp evap Temp comp T cond evap P cond P comp % COP/ Composition (%)outlet (° C.) outlet (° C.) outlet (° C.) (bar) (bar) Ratio (w/w) Glideefficiency % CAP COPLorenz HFC-134a −5 81 50 2.4 13.2 5.4 0.00 75.9 10054 HFO- HFO- HFC-32 1243zf 1234ze 5 90 5 −3 74 46 2.6 12.1 4.6 2.04 79.0103 57 5 80 15 −3 74 46 2.6 12.1 4.7 2.18 78.9 103 57 5 70 25 −3 74 462.5 12.0 4.7 2.28 78.7 102 57 5 60 35 −3 74 46 2.5 11.9 4.8 2.34 78.5101 57 5 50 45 −3 74 46 2.4 11.8 4.8 2.40 78.4 100 57 5 40 55 −3 74 462.4 11.6 4.9 2.45 78.2 98 56 15 80 5 0 77 42 3.4 13.9 4.1 5.30 80.6 13759 15 70 15 0 78 42 3.3 13.9 4.2 5.48 80.5 138 60 15 60 25 1 78 42 3.313.8 4.2 5.57 80.4 137 60 15 50 35 1 78 43 3.2 13.7 4.2 5.62 80.4 135 6015 40 45 1 78 43 3.2 13.5 4.2 5.66 80.3 133 60 15 30 55 1 78 43 3.1 13.34.3 5.73 80.2 131 59 15 20 65 1 79 43 3.1 13.2 4.3 5.84 80.1 129 59 1510 75 1 79 43 3.0 13.1 4.4 6.01 80.0 128 59

Example 5: Results for a Moderate-Temperature Heating, Comparison withHFC-134a

HFC-32/HFC-152a/HFO-1243zf mixture:

Temp evap Temp comp T cond evap P cond P comp % COPc/ Composition (%)outlet (° C.) outlet (° C.) outlet (° C.) (bar) (bar) Ratio (w/w) Glideefficiency % CAPc COPLorenz R134a −5 81 50 2.4 13.2 5.4 0.00 75.9 100 63HFC- HFO- HFC-32 152a 1243zf 5 5 90 −3 75 47 2.6 12.3 4.7 1.82 78.9 10266 5 15 80 −3 78 47 2.6 12.5 4.8 1.65 78.5 104 66 5 25 70 −3 81 47 2.612.6 4.9 1.54 78.2 105 66 5 35 60 −4 84 47 2.6 12.7 4.9 1.46 78.0 106 665 45 50 −4 86 47 2.6 12.7 5.0 1.38 77.7 107 66 5 55 40 −4 89 48 2.5 12.75.0 1.31 77.6 107 66 5 65 30 −4 91 48 2.5 12.7 5.1 1.22 77.4 107 66 5 7520 −4 93 48 2.5 12.6 5.1 1.11 77.2 106 66 5 85 10 −4 95 48 2.4 12.5 5.20.97 76.9 106 66 15 5 80 0 79 42 3.3 14.0 4.2 4.79 80.4 129 67 15 15 70−1 82 43 3.3 14.1 4.3 4.31 80.0 129 67 15 25 60 −1 85 43 3.2 14.2 4.44.02 79.7 129 67 15 35 50 −1 87 44 3.1 14.2 4.5 3.81 79.4 129 67 15 4540 −1 90 44 3.1 14.2 4.6 3.64 79.2 129 67 15 55 30 −2 93 44 3.0 14.1 4.73.47 78.9 128 67 15 65 20 −2 95 44 2.9 14.0 4.8 3.27 78.6 127 67 15 7510 −2 98 44 2.8 13.8 4.9 3.02 78.3 126 67

HFO-1234yf/HFC-32/HFO-1243zf mixture:

Temp evap Temp comp T cond evap P cond P comp % COP/ Composition (%)outlet (° C.) outlet (° C.) outlet (° C.) (bar) (bar) Ratio (w/w) Glideefficiency % CAP COPLorenz R134a −5 81 50 2.4 13.2 5.4 0.00 75.9 100 63HFO- HFO- 1234yf HFC-32 1243zf 5 5 90 −3 73 46 2.6 12.2 4.6 1.93 79.1102 66 15 5 80 −3 72 46 2.7 12.4 4.6 1.92 79.2 102 65 25 5 70 −3 72 462.7 12.6 4.6 1.92 79.2 103 65 35 5 60 −3 72 46 2.8 12.8 4.6 1.94 79.2104 64 45 5 50 −3 71 46 2.8 13.0 4.6 1.97 79.2 105 64 55 5 40 −3 71 462.9 13.2 4.6 1.99 79.2 107 64 65 5 30 −3 71 46 2.9 13.5 4.6 2.00 79.2108 64 75 5 20 −3 70 46 3.0 13.7 4.6 1.97 79.2 109 64 5 15 80 0 77 423.4 14.0 4.1 5.12 80.7 131 67 15 15 70 0 76 42 3.5 14.3 4.1 5.07 80.7133 67 25 15 60 0 76 42 3.6 14.6 4.1 5.07 80.7 135 67 35 15 50 0 76 423.6 14.9 4.1 5.08 80.7 137 67 45 15 40 0 76 42 3.7 15.2 4.1 5.07 80.6139 66 55 15 30 0 75 42 3.8 15.6 4.1 5.02 80.6 140 66 65 15 20 0 75 423.8 15.9 4.1 4.93 80.6 141 65 75 15 10 0 75 43 3.9 16.2 4.1 4.82 80.6142 64

HFC-32/HFO-1243zf/HFO-1234ze mixture:

Temp evap Temp comp T cond evap P cond P comp % COPc/ Composition (%)outlet (° C.) outlet (° C.) outlet (° C.) (bar) (bar) Ratio (w/w) Glideefficiency % CAP COPLorenz HFC-134a −5 81 50 2.4 13.2 5.4 0.00 75.9 10063 HFC- HFO- HFC-32 1243zf 1234ze 5 90 5 −3 74 46 2.6 12.1 4.6 2.04 79.0101 66 5 80 15 −3 74 46 2.6 12.1 4.7 2.18 78.9 101 66 5 70 25 −3 74 462.5 12.0 4.7 2.28 78.7 100 66 5 60 35 −3 74 46 2.5 11.9 4.8 2.34 78.5 9966 15 80 5 0 77 42 3.4 13.9 4.1 5.30 80.6 130 67 15 70 15 0 78 42 3.313.9 4.2 5.48 80.5 130 67 15 60 25 1 78 42 3.3 13.8 4.2 5.57 80.4 130 6815 50 35 1 78 43 3.2 13.7 4.2 5.62 80.4 128 68 15 40 45 1 78 43 3.2 13.54.2 5.66 80.3 126 68 15 30 55 1 78 43 3.1 13.3 4.3 5.73 80.2 125 68 1520 65 1 79 43 3.1 13.2 4.3 5.84 80.1 123 67 15 10 75 1 79 43 3.0 13.14.4 6.01 80.0 122 67 25 70 5 2 82 41 4.1 15.9 3.9 6.91 81.2 157 67 25 6015 2 82 41 4.0 15.9 3.9 6.98 81.1 156 68 25 50 25 2 82 41 4.0 15.7 4.07.01 81.0 155 68 25 40 35 2 82 41 3.9 15.5 4.0 7.04 81.0 153 68 25 30 452 82 41 3.8 15.3 4.0 7.09 81.0 151 68 25 20 55 2 82 41 3.8 15.1 4.0 7.1880.9 148 68 25 10 65 2 83 41 3.7 15.1 4.1 7.31 80.8 147 67

Example 6: Results for a Moderate-Temperature Cooling, Comparison withR404a and R407c

HFC-32/HFC-152a/HFO-1243zf mixture:

Temp evap Temp comp T cond evap P comp % COP/ Composition (%) outlet (°C.) outlet (° C.) outlet (° C.) (bar) cond P (bar) Ratio (w/w) Glideefficiency % CAP COPLorenz R404A −5 77 50 5.2 23.0 4.5 0.37 79.7 100 48R407C −1 89 45 4.5 19.8 4.4 4.46 79.9 114 56 HFC- HFO- HFC-32 152a1243zf 25 5 70 1 83 41 4.0 15.9 3.9 6.41 81.1 105 59 25 15 60 1 86 413.9 16.0 4.1 5.65 80.6 100 57 25 25 50 0 89 42 3.8 16.0 4.2 5.39 80.3101 58 25 35 40 0 92 42 3.7 15.9 4.3 5.19 80.1 102 59 25 45 30 0 95 423.6 15.8 4.4 5.05 79.8 102 59 25 55 20 0 98 42 3.5 15.6 4.5 4.93 79.5101 60 25 65 10 0 100 42 3.4 15.4 4.6 4.78 79.2 100 60 35 5 60 2 88 414.6 18.1 3.9 6.67 81.2 119 59 35 15 50 1 92 41 4.4 18.0 4.1 6.09 80.8115 57 35 25 40 1 95 42 4.3 17.9 4.2 5.85 80.5 115 58 35 35 30 1 98 424.2 17.8 4.3 5.76 80.2 115 58 35 45 20 1 101 42 4.0 17.5 4.3 5.80 80.0115 59 35 55 10 1 104 42 3.9 17.2 4.4 5.87 79.7 114 60 50 5 45 1 98 435.4 21.6 4.0 5.61 80.9 136 57 50 15 35 0 101 43 5.1 21.3 4.2 5.50 80.5134 57 50 25 25 1 105 43 4.9 21.0 4.3 5.55 80.3 132 57 50 35 15 1 108 434.8 20.7 4.3 5.85 80.0 132 58 50 45 5 1 111 43 4.6 20.2 4.4 6.31 79.8132 58

HFO-1234yf/HFC-32/HFO-1243zf mixture:

Temp evap Temp comp T cond evap P comp % COP/ Composition (%) outlet (°C.) outlet (° C.) outlet (° C.) (bar) cond P (bar) Ratio (w/w) Glideefficiency % CAP COPLorenz R404A −5 77 50 5.2 23.0 4.5 0.37 79.7 100 48R407C −1 89 45 4.5 19.8 4.4 4.46 79.9 114 56 HFO- HFC- HFO- 1234yf 321243zf 5 25 70 2 81 40 4.2 16.0 3.9 6.76 81.3 107 60 15 25 60 2 80 404.2 16.4 3.9 6.65 81.2 109 59 25 25 50 2 80 41 4.3 16.8 3.9 6.55 81.2110 59 35 25 40 1 80 41 4.4 17.2 3.9 6.43 81.1 111 58 45 25 30 1 80 414.5 17.7 3.9 6.25 81.1 112 58 55 25 20 1 80 42 4.6 18.2 4.0 6.02 81.0112 57 65 25 10 1 80 43 4.7 18.6 4.0 5.77 81.0 112 57 5 35 60 2 86 414.8 18.3 3.8 6.94 81.3 123 59 15 35 50 2 86 41 4.9 18.8 3.8 6.73 81.3124 59 25 35 40 1 86 42 5.0 19.3 3.9 6.47 81.2 125 58 35 35 30 1 86 425.1 19.9 3.9 6.16 81.1 125 57 45 35 20 1 87 43 5.2 20.4 4.0 5.78 81.0125 57 5 50 45 0 96 43 5.5 22.0 4.0 5.48 81.0 139 58 15 50 35 0 96 445.6 22.6 4.0 5.05 80.9 139 57 50 50 0 −2 96 47 6.0 24.9 4.2 3.36 80.5 5430 70 0 −4 110 49 6.5 28.4 4.4 1.15 75.9 53

The last two lines of the table provide a comparative example (binarymixtures resulting from document WO 2009/150763, less effective than theternary mixtures according to the invention).

HFC-32/HFO-1243zf/HFO-1234ze mixture:

Temp evap Temp comp T cond evap P cond P comp % COP/ Composition (%)outlet (° C.) outlet (° C.) outlet (° C.) (bar) (bar) Ratio (w/w) Glideefficiency % CAP COPLorenz R404A −5 77 50 5.2 23.0 4.5 0.37 79.7 100 48R407C −1 89 45 4.5 19.8 4.4 4.46 79.9 114 56 HFO- HFO- HFC-32 1243zf1234ze 25 70 5 2 82 41 4.1 15.9 3.9 6.91 81.2 107 60 25 60 15 2 82 414.0 15.9 3.9 6.98 81.1 107 60 25 50 25 2 82 41 4.0 15.7 4.0 7.01 81.0106 60 25 40 35 2 82 41 3.9 15.5 4.0 7.04 81.0 105 61 25 30 45 2 82 413.8 15.3 4.0 7.09 81.0 103 61 25 20 55 2 82 41 3.8 15.1 4.0 7.18 80.9101 61 25 10 65 2 83 41 3.7 15.1 4.1 7.31 80.8 100 60 35 60 5 2 87 414.7 18.1 3.8 7.09 81.3 122 60 35 50 15 2 87 41 4.6 18.0 3.9 7.16 81.2121 60 35 40 25 2 87 41 4.6 17.7 3.9 7.24 81.2 121 60 35 30 35 2 87 414.5 17.4 3.9 7.35 81.2 119 61 35 20 45 2 87 41 4.4 17.1 3.9 7.47 81.2118 61 35 10 55 3 87 41 4.3 17.1 3.9 7.59 81.1 116 60 50 45 5 1 96 435.5 21.6 4.0 5.83 81.0 138 58 50 35 15 1 96 43 5.4 21.2 4.0 6.17 81.0138 58 50 25 25 2 96 42 5.3 20.7 3.9 6.52 81.1 138 59 50 15 35 2 96 425.2 20.4 3.9 6.83 81.1 137 59 50 5 45 2 96 42 5.1 20.3 4.0 7.05 81.0 13659

Example 7: Results for a Moderate-Temperature Heating, Comparison withR404a and R407c

HFC-32/HFC-152a/HFO-1243zf mixture:

Temp evap Temp comp T cond Ratio comp % COPc/ Composition (%) outlet (°C.) outlet (° C.) outlet (° C.) evap P (bar) cond P (bar) (w/w) Glideefficiency % CAPc COPLorenz R404A −5 77 50 5.2 23.0 4.5 0.37 79.7 100 58R407C −1 89 45 4.5 19.8 4.4 4.46 79.9 107 64 HFC- HFO- HFC-32 152a1243zf 25 5 70 1 83 41 4.0 15.9 3.9 6.41 81.1 96 67 35 5 60 2 88 41 4.618.1 3.9 6.67 81.2 109 66 35 15 50 1 92 41 4.4 18.0 4.1 6.09 80.8 107 6635 25 40 1 95 42 4.3 17.9 4.2 5.85 80.5 106 66 35 35 30 1 98 42 4.2 17.84.3 5.76 80.2 106 66 35 45 20 1 101 42 4.0 17.5 4.3 5.80 80.0 105 67 3555 10 1 104 42 3.9 17.2 4.4 5.87 79.7 104 67 50 5 45 1 98 43 5.4 21.64.0 5.61 80.9 125 65 50 15 35 0 101 43 5.1 21.3 4.2 5.50 80.5 123 65 5025 25 1 105 43 4.9 21.0 4.3 5.55 80.3 122 65 50 35 15 1 108 43 4.8 20.74.3 5.85 80.0 121 65 50 45 5 1 111 43 4.6 20.2 4.4 6.31 79.8 119 65

HFO-1234yf/HFC-32/HFO-1243zf mixture:

Temp evap Temp comp T cond evap P cond P Ratio comp % % COP/ Composition(%) outlet (° C.) outlet (° C.) outlet (° C.) (bar) (bar) (w/w) Glideefficiency CAPc COPLorenz R404A −5 77 50 5.2 23.0 4.5 0.37 79.7 100 58R407C −1 89 45 4.5 19.8 4.4 4.46 79.9 107 64 HFO- HFO- 1234yf HFC-321243zf 5 25 70 2 81 40 4.2 16.0 3.9 6.76 81.3 98 67 15 25 60 2 80 40 4.216.4 3.9 6.65 81.2 99 67 25 25 50 2 80 41 4.3 16.8 3.9 6.55 81.2 101 6735 25 40 1 80 41 4.4 17.2 3.9 6.43 81.1 102 66 45 25 30 1 80 41 4.5 17.73.9 6.25 81.1 102 65 55 25 20 1 80 42 4.6 18.2 4.0 6.02 81.0 103 65 5 3560 2 86 41 4.8 18.3 3.8 6.94 81.3 112 67 15 35 50 2 86 41 4.9 18.8 3.86.73 81.3 113 66 25 35 40 1 86 42 5.0 19.3 3.9 6.47 81.2 113 65

HFC-32/HFO-1243zf/HFO-1234ze mixture:

Temp evap Temp comp T cond Ratio comp % COPc/ Composition (%) outlet (°C.) outlet (° C.) outlet (° C.) evap P (bar) cond P (bar) (w/w) Glideefficiency % CAP COPLorenz R404A −5 77 50 5.2 23.0 4.5 0.37 79.7 100 58R407C −1 89 45 4.5 19.8 4.4 4.46 79.9 107 64 HFO- HFO- HFC-32 1243zf1234ze 35 60 5 2 87 41 4.7 18.1 3.8 7.09 81.3 111 67 35 50 15 2 87 414.6 18.0 3.9 7.16 81.2 110 67 35 40 25 2 87 41 4.6 17.7 3.9 7.24 81.2109 67 35 30 35 2 87 41 4.5 17.4 3.9 7.35 81.2 108 68 35 20 45 2 87 414.4 17.1 3.9 7.47 81.2 106 68 35 10 55 3 87 41 4.3 17.1 3.9 7.59 81.1105 67 50 45 5 1 96 43 5.5 21.6 4.0 5.83 81.0 127 65 50 35 15 1 96 435.4 21.2 4.0 6.17 81.0 126 66 50 25 25 2 96 42 5.3 20.7 3.9 6.52 81.1125 66 50 15 35 2 96 42 5.2 20.4 3.9 6.83 81.1 124 66 50 5 45 2 96 425.1 20.3 4.0 7.05 81.0 123 66 65 10 25 0 106 44 5.9 23.9 4.1 5.18 80.7138 65

Example 8: Results for a Moderate-Temperature Cooling, Comparison withR410a

HFC-32/HFC-152a/HFO-1243zf mixture:

Temp evap Temp comp T cond evap P cond P Ratio comp % COP/ Composition(%) outlet (° C.) outlet (° C.) outlet (° C.) (bar) (bar) (w/w) Glideefficiency % CAP COPLorenz R410A −5 103 50 6.8 30.7 4.5 0.07 79.5 100 50HFC- HFO- HFC-32 152a 1243zf 65 5 30 −1 109 46 5.9 25.2 4.3 3.76 80.3 9955 65 15 20 −1 112 46 5.7 24.7 4.4 4.20 80.0 98 55 65 25 10 0 116 46 5.424.1 4.4 4.84 79.7 97 56 80 5 15 −3 120 48 6.3 28.3 4.5 2.06 79.6 106 5480 15 5 −2 124 48 6.1 27.5 4.5 3.17 79.4 105 54 90 5 5 −4 127 49 6.629.8 4.5 1.35 79.4 110 53

HFO-1234yf/HFC-32/HFO-1243zf mixture:

Temp evap Temp comp T cond Ratio comp % COP/ Composition (%) outlet (°C.) outlet (° C.) outlet (° C.) evap P (bar) cond P (bar) (w/w) Glideefficiency % CAP COPLorenz R410A −5 103 50 6.8 30.7 4.5 0.07 79.5 100 50HFO- HFO- 1234yf HFC-32 1243zf 5 65 30 −2 107 46 6.1 25.8 4.2 3.17 80.4100 55 15 65 20 −2 107 47 6.2 26.4 4.3 2.60 80.2 99 54 25 65 10 −3 10748 6.3 27.1 4.3 2.03 80.1 98 53 5 80 15 −4 118 49 6.5 29.0 4.4 1.12 79.7105 53 15 80 5 −4 117 49 6.6 29.5 4.4 0.66 79.7 106 53

HFC-32/HFO-1243zf/HFO-1234ze mixture:

Temp evap Temp comp T cond Ratio comp % COP/ Composition (%) outlet (°C.) outlet (° C.) outlet (° C.) evap P (bar) cond P (bar) (w/w) Glideefficiency % CAP COPLorenz R410A −5 103 50 6.8 30.7 4.5 0.07 79.5 100 50HFO- HFO- HFC-32 1243zf 1234ze 65 30 5 −1 107 46 6.0 25.2 4.2 3.85 80.5100 56 65 20 15 0 106 45 5.9 24.4 4.1 4.59 80.6 101 57 65 10 25 0 106 445.9 23.9 4.1 5.18 80.7 101 57 80 15 5 −3 118 48 6.4 28.3 4.4 1.97 79.9107 54 80 5 15 −2 117 47 6.4 27.5 4.3 2.87 80.1 107 55 90 5 5 −4 125 496.7 29.9 4.5 1.00 79.6 110 54

Example 9: Results for a Moderate-Temperature Heating, Comparison withR410a

HFC-32/HFC-152a/HFO-1243zf mixture:

Temp evap Temp comp T cond Ratio comp % COPc/ Composition (%) outlet (°C.) outlet (° C.) outlet (° C.) evap P (bar) cond P (bar) (w/w) Glideefficiency % CAPc COPLorenz R410A −5 103 50 6.8 30.7 4.5 0.07 79.5 10059 HFC- HFO- HFC-32 152a 1243zf 65 5 30 −1 109 46 5.9 25.2 4.3 3.76 80.395 63 80 5 15 −3 120 48 6.3 28.3 4.5 2.06 79.6 103 62 80 15 5 −2 124 486.1 27.5 4.5 3.17 79.4 102 62

HFO-1234yf/HFC-32/HFO-1243zf mixture:

Temp evap Temp comp T cond Ratio comp % COP/ Composition (%) outlet (°C.) outlet (° C.) outlet (° C.) evap P (bar) cond P (bar) (w/w) Glideefficiency % CAP COPLorenz R410A −5 103 50 6.8 30.7 4.5 0.07 79.5 100 59HFO- HFO- 1234yf HFC-32 1243zf  5 80 15 −4 118 49 6.5 29.0 4.4 1.12 79.7104 61 15 80 5 −4 117 49 6.6 29.5 4.4 0.66 79.7 104 61

HFC-32/HFO-1243zf/HFO-1234ze mixture:

Temp evap Temp comp T cond Ratio comp % COPc/ Composition (%) outlet (°C.) outlet (° C.) outlet (° C.) evap P (bar) cond P (bar) (w/w) Glideefficiency % CAP COPLorenz R410A −5 103 50 6.8 30.7 4.5 0.07 79.5 100 59HFO- HFO- HFC-32 1243zf 1234ze 80 15 5 −3 118 48 6.4 28.3 4.4 1.97 79.9104 62 80 5 15 −2 117 47 6.4 27.5 4.3 2.87 80.1 103 63

Example 10: Results for a Low-Temperature Refrigeration, Comparison withHFC-32

HFO-1234yf/HFC-32/HFO-1243zf mixture:

Temp evap Temp comp T cond Ratio comp % COP/ Composition (%) outlet (°C.) outlet (° C.) outlet (° C.) evap P (bar) cond P (bar) (w/w) Glideefficiency % CAP COPLorenz R32 −30 215 40 2.7 24.8 9.0 0.0 51.6 100 34HFO- HFO- 1234yf HFC-32 1243zf 23 75 2 −29 172 39 2.6 22.9 8.7 0.8 54.291 36 21 75 4 −29 173 39 2.6 22.8 8.8 1.0 54.0 91 36 19 75 6 −29 173 392.6 22.8 8.8 1.1 53.9 90 35 17 75 8 −29 174 39 2.6 22.7 8.8 1.2 53.8 9035 18 80 2 −29 180 39 2.6 23.4 8.8 0.5 53.5 93 35 16 80 4 −29 181 39 2.623.3 8.8 0.7 53.4 93 35 14 80 6 −29 182 39 2.6 23.2 8.9 0.8 53.2 92 3512 80 8 −29 183 39 2.6 23.2 8.9 0.9 53.1 92 35 10 80 10 −29 184 39 2.623.1 8.9 1.0 53.0 92 35 12 86 2 −30 191 40 2.7 23.9 8.9 0.3 52.8 95 3510 86 4 −30 192 40 2.7 23.8 8.9 0.4 52.7 95 35 8 86 6 −29 193 39 2.723.7 8.9 0.5 52.5 95 35 8 90 2 −30 198 40 2.7 24.1 9.0 0.2 52.4 96 35

Example 11: Results for a Moderate-Temperature Cooling, Comparison withHFC-32

HFO-1234yf/HFC-32/HFO-1243zf mixture:

Temp evap Temp comp T cond Ratio comp % COP/ Composition (%) outlet (°C.) outlet (° C.) outlet (° C.) evap P (bar) cond P (bar) (w/w) Glideefficiency % CAP COPLorenz R32 −5 132 50 6.9 31.4 4.6 0.0 79.3 100 53HFO- HFO- 1234yf HFC-32 1243zf 23 75 2 −4 114 49 6.6 29.0 4.4 0.84 79.891 53 21 75 4 −4 114 49 6.6 28.9 4.4 0.92 79.8 90 53 19 75 6 −4 114 496.5 28.8 4.4 1.00 79.8 90 53 18 80 2 −4 117 49 6.7 29.6 4.4 0.55 79.7 9353 16 80 4 −4 117 49 6.6 29.5 4.4 0.62 79.7 92 53 14 80 6 −4 117 49 6.629.4 4.4 0.70 79.7 92 53 12 80 8 −4 117 49 6.6 29.3 4.4 0.79 79.7 92 5310 80 10 −4 118 49 6.6 29.2 4.4 0.88 79.7 92 53 8 80 12 −4 118 49 6.629.1 4.4 0.97 79.7 92 53 6 80 14 −4 118 49 6.5 29.0 4.4 1.07 79.7 92 534 80 16 −4 118 49 6.5 28.9 4.4 1.17 79.7 92 53 2 80 18 −4 118 49 6.528.8 4.4 1.28 79.7 92 53 12 86 2 −5 122 50 6.7 30.2 4.5 0.30 79.6 95 5310 86 4 −5 122 49 6.7 30.2 4.5 0.37 79.6 95 53 8 86 6 −5 122 49 6.7 30.14.5 0.44 79.6 95 53 6 86 8 −4 122 49 6.7 30.0 4.5 0.52 79.6 95 53 4 8610 −4 122 49 6.7 29.9 4.5 0.61 79.6 95 53 2 86 12 −4 122 49 6.6 29.8 4.50.69 79.6 95 53

Example 12: Results for a Moderate-Temperature Heating, Comparison withHFC-32

HFO-1234yf/HFC-32/HFO-1243zf mixture:

Temp evap Temp comp T cond Ratio comp % COP/ Composition (%) outlet (°C.) outlet (° C.) outlet (° C.) evap P (bar) cond P (bar) (w/w) Glideefficiency % CAP COPLorenz R32 −5 132 50 6.9 31.4 4.6 0.0 79.3 100 61HFO- HFO- 1234yf HFC-32 1243zf 23 75 2 −4 114 49 6.6 29.0 4.4 0.84 79.891 61 21 75 4 −4 114 49 6.6 28.9 4.4 0.92 79.8 91 61 19 75 6 −4 114 496.5 28.8 4.4 1.00 79.8 91 61 18 80 2 −4 117 49 6.7 29.6 4.4 0.55 79.7 9361 16 80 4 −4 117 49 6.6 29.5 4.4 0.62 79.7 93 61 14 80 6 −4 117 49 6.629.4 4.4 0.70 79.7 93 61 12 80 8 −4 117 49 6.6 29.3 4.4 0.79 79.7 93 6112 86 2 −5 122 50 6.7 30.2 4.5 0.30 79.6 95 61 10 86 4 −5 122 49 6.730.2 4.5 0.37 79.6 95 61 8 86 6 −5 122 49 6.7 30.1 4.5 0.44 79.6 95 61 686 8 −4 122 49 6.7 30.0 4.5 0.52 79.6 95 61 4 86 10 −4 122 49 6.7 29.94.5 0.61 79.6 95 61 2 86 12 −4 122 49 6.6 29.8 4.5 0.69 79.6 95 61

Example 13: Data Regarding the Quasi-Azeotropic Mixtures

HFC-32/HFC-152a/HFO-1243zf mixture:

Psat Psat HFO- Temperature liquid vapor % diff in HFC-32 HFC-152a 1243zf(° C.) (bar) (bar) pressure 75 2 23 −5 6.4 5.8 9 80 2 18 −5 6.5 6.1 7 869 5 −5 6.5 5.9 9 86 2 12 −5 6.6 6.3 5 90 8 2 −5 6.6 6.1 7 90 5 5 −5 6.66.3 5 90 2 8 −5 6.7 6.5 3

HFO-1234yf/HFC-32/HFO-1243zf mixture:

Psat Psat HFO- Temperature liquid vapor % diff in 1234yf HFC-32HFO-1243zf (° C.) (bar) (bar) pressure 28 70 2 −5 6.5 6.2 5 20 70 10 −56.5 6.1 6 10 70 20 −5 6.4 5.9 8 23 75 2 −5 6.6 6.4 3 20 75 5 −5 6.6 6.34 10 75 15 −5 6.5 6.1 6 2 75 23 −5 6.5 6.0 7 18 80 2 −5 6.7 6.5 2 15 805 −5 6.7 6.5 3 10 80 10 −5 6.6 6.4 4 2 80 18 −5 6.6 6.2 5 12 86 2 −5 6.86.7 1 9 86 5 −5 6.7 6.6 2 2 86 12 −5 6.7 6.5 3 8 90 2 −5 6.8 6.7 1 5 905 −5 6.8 6.7 1 2 90 8 −5 6.8 6.6 2

HFC-32/HFO-1243zf/HFO-1234ze mixture:

Psat Psat HFO- Temperature liquid vapor % diff in HFC-32 HFO-1243zf1234ze (° C.) (bar) (bar) pressure 75 23 2 −5 6.4 5.9 9 80 10 10 −5 6.55.9 9 80 18 2 −5 6.5 6.1 6 86 2 12 −5 6.6 6.1 7 86 5 9 −5 6.6 6.2 7 8612 2 −5 6.7 6.4 4 90 2 8 −5 6.7 6.4 5 90 5 5 −5 6.7 6.5 4 90 8 2 −5 6.76.5 3

The invention claimed is:
 1. A ternary composition comprising:difluoromethane; 3,3,3-trifluoropropene; and 2,3,3,3-tetrafluoropropene,wherein the ternary composition is selected from one of the followingcompositions: a ternary composition comprising: from 25 to 50% ofdifluoromethane; from 2 to 65% of 3,3,3-trifluoropropene; and from 10 to70% of 2,3,3,3-tetrafluoropropene, a ternary composition comprising:from 65 to 80% of difluoromethane; from 2 to 15% of3,3,3-trifluoropropene; and from 5 to 30% of 2,3,3,3-tetrafluoropropene,a ternary composition comprising: from 25 to 35% of difluoromethane;from 2 to 70% of 3,3,3-trifluoropropene; and from 5 to 65% of2,3,3,3-tetrafluoropropene, a ternary composition comprising: from 65 to80% of difluoromethane; from 5 to 30% of 3,3,3-trifluoropropene; andfrom 5 to 25% of 2,3,3,3-tetrafluoropropene, a ternary compositioncomprising: from 75 to 90% of difluoromethane; from 2 to 10% of3,3,3-trifluoropropene; and from 8 to 23% of 2,3,3,3-tetrafluoropropene,a ternary composition comprising: from 75 to 90% of difluoromethane;from 2 to 18% of 3,3,3-trifluoropropene; and from 2 to 23% of2,3,3,3-tetrafluoropropene, and a ternary composition comprising: from70 to 98% of difluoromethane; from 1 to 23% of 3,3,3-trifluoropropene;and from 1 to 28% of 2,3,3,3-tetrafluoropropene.
 2. The composition asclaimed in claim 1 comprising: from 25 to 50% of difluoromethane; from 2to 65% of 3,3,3-trifluoropropene; and from 10 to 70% of2,3,3,3-tetrafluoropropene.
 3. The composition as claimed in claim 1comprising: from 65 to 80% of difluoromethane; from 2 to 15% of3,3,3-trifluoropropene; and from 5 to 30% of 2,3,3,3-tetrafluoropropene.4. The composition as claimed in claim 1 comprising: from 25 to 35% ofdifluoromethane; from 2 to 70% of 3,3,3-trifluoropropene; and from 5 to65% of 2,3,3,3-tetrafluoropropene.
 5. The composition as claimed inclaim 1 comprising: from 65 to 80% of difluoromethane; from 5 to 30% of3,3,3-trifluoropropene; and from 5 to 25% of 2,3,3,3-tetrafluoropropene.6. The composition as claimed in claim 1 comprising: from 75 to 90% ofdifluoromethane; from 2 to 10% of 3,3,3-trifluoropropene; and from 8 to23% of 2,3,3,3-tetrafluoropropene.
 7. The composition as claimed inclaim 1 comprising: from 75 to 90% of difluoromethane; from 2 to 18% of3,3,3-trifluoropropene; and from 2 to 23% of 2,3,3,3-tetrafluoropropene.8. The composition as claimed in claim 1 comprising: from 70 to 98% ofdifluoromethane; from 1 to 23% of 3,3,3-trifluoropropene; and from 1 to28% of 2,3,3,3-tetrafluoropropene.
 9. A heat-transfer compositioncomprising the composition as claimed in claim 1, the heat-transfercomposition further comprising one or more additives selected from thegroup consisting of lubricants, stabilizers, surfactants, tracers,fluorescent agents, odorous agents, solubilizing agents and mixturesthereof.
 10. A heat-transfer composition consisting of the compositionas claimed in claim 1 and optionally one or more additives selected fromthe group consisting of lubricants, stabilizers, surfactants, tracers,fluorescent agents, odorous agents, solubilizing agents and mixturesthereof.
 11. Heat-transfer equipment comprising a vapor compressioncircuit containing a composition as claimed in claim
 10. 12. A vaporcompression circuit comprising the composition as claimed in claim 1.13. The vapor compression circuit as claimed in claim 12, comprising acountercurrent heat exchanger.
 14. Heat-transfer equipment comprising avapor compression circuit containing a composition as claimed inclaim
 1. 15. The equipment as claimed in claim 14, comprising acountercurrent heat exchanger.
 16. A process for heating or cooling afluid or a body by means of a vapor compression circuit containing aheat-transfer fluid, said process successively comprising theevaporation of the heat-transfer fluid, the compression of theheat-transfer fluid, the condensation of the heat fluid and theexpansion of the heat-transfer fluid, in which the heat-transfer fluidis a composition as claimed in claim
 1. 17. A process for cooling afluid or a body by means of a vapor compression circuit containing aheat-transfer fluid, said process successively comprising theevaporation of the heat-transfer fluid, the compression of theheat-transfer fluid, the condensation of the heat fluid and theexpansion of the heat-transfer fluid, in which the temperature of thefluid or the body cooled is from −40° C. to −10° C., and in which theheat-transfer fluid is a ternary composition comprising: from 58 to 90%of difluoromethane, 2 to 40% of 3,3,3-trifluoropropene, and from 2 to40% of 2,3,3,3-tetrafluoropropene; or from 68 to 96% of difluoromethane,from 2 to 20% of 3,3,3-trifluoropropene, and from 2 to 30% of2,3,3,3-tetrafluoropropene.
 18. A process for cooling a fluid or a bodyby means of a vapor compression circuit containing a heat-transferfluid, said process successively comprising the evaporation of theheat-transfer fluid, the compression of the heat-transfer fluid, thecondensation of the heat fluid and the expansion of the heat-transferfluid, in which the temperature of the fluid or of the body cooled isfrom −15° C. to 15° C., and in which the heat-transfer fluid is aternary composition comprising: from 60 to 90% of difluoromethane, from2 to 30% of 3,3,3-trifluoropropene, and from 2 to 30% of2,3,3,3-tetrafluoropropene; or from 58 to 90% of difluoromethane, from 2to 40% of 3,3,3-trifluoropropene, and from 2 to 40% of2,3,3,3-tetrafluoropropene.
 19. A process for heating a fluid or a bodyby means of a vapor compression circuit containing a heat-transferfluid, said process successively comprising the evaporation of theheat-transfer fluid, the compression of the heat-transfer fluid, thecondensation of the heat fluid and the expansion of the heat-transferfluid, in which the temperature of the fluid or of the body heated isfrom 30° C. to 80° C., and in which the heat-transfer fluid is a ternarycomposition comprising: from 60 to 90% of difluoromethane, from 2 to 30%of 3,3,3-trifluoropropene, and from 2 to 30% of2,3,3,3-tetrafluoropropene; or from 58 to 90% of difluoromethane, from 2to 40% of 3,3,3-trifluoropropene, and from 2 to 40% of2,3,3,3-tetrafluoropropene.
 20. A process for reducing the environmentalimpact of a heat-transfer equipment comprising a vapor compressioncircuit containing an initial heat-transfer fluid, said processcomprising a step of replacing the initial heat-transfer fluid in thevapor compression circuit with a final transfer fluid, the finaltransfer fluid having a GWP lower than the initial heat-transfer fluid,in which the final heat-transfer fluid is a composition as claimed inclaim
 1. 21. A process for reducing the environmental impact of aheat-transfer equipment comprising a vapor compression circuitcontaining an initial heat-transfer fluid, said process comprising astep of replacing the initial heat-transfer fluid in the vaporcompression circuit with a final transfer fluid, the final transferfluid having a GWP lower than the initial heat-transfer fluid, in whichthe initial heat-transfer fluid is a binary mixture of 50% ofdifluoromethane and 50% of pentafluoroethane, and in which the finalheat-transfer fluid is a ternary composition comprising: from 58 to 90%of difluoromethane, from 2 to 40% of 3,3,3-trifluoropropene, and from 2to 40% of 2,3,3,3-tetrafluoropropene.
 22. A process for reducing theenvironmental impact of a heat-transfer equipment comprising a vaporcompression circuit containing an initial heat-transfer fluid, saidprocess comprising a step of replacing the initial heat-transfer fluidin the vapor compression circuit with a final transfer fluid, the finaltransfer fluid having a GWP lower than the initial heat-transfer fluid,in which the initial heat-transfer fluid is difluoromethane, and inwhich the final heat-transfer fluid is a ternary composition comprising:from 68 to 96% of difluoromethane, from 2 to 20% of3,3,3-trifluoropropene, and from 2 to 30% of 2,3,3,3-tetrafluoropropene.